CN115353657A - Preparation method of magnetic field induced organic-inorganic composite cross-linked anion exchange membrane - Google Patents
Preparation method of magnetic field induced organic-inorganic composite cross-linked anion exchange membrane Download PDFInfo
- Publication number
- CN115353657A CN115353657A CN202210976489.0A CN202210976489A CN115353657A CN 115353657 A CN115353657 A CN 115353657A CN 202210976489 A CN202210976489 A CN 202210976489A CN 115353657 A CN115353657 A CN 115353657A
- Authority
- CN
- China
- Prior art keywords
- solution
- hydrotalcite
- quaternized
- ferroferric oxide
- anion exchange
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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 the hydrotalcite-coated ferroferric oxide to obtain a dispersion liquid, and dissolving a quaternized polymer to obtain a quaternized polymer solution; (3) Adding the inorganic matter dispersion liquid and the polyvinyl alcohol solution into the quaternary ammonium polymer solution and fully mixing to obtain a membrane casting solution; (4) And casting the casting solution on a glass plate, putting the whole body in a magnetic field environment, carrying out crosslinking reaction and evaporating the solvent to dryness to obtain the silicon-based solar cell module. The invention takes quaternized polyphenyl ether as an anion exchange membrane substrate, and loads hydrotalcite on Fe 3 O 4 In addition, the agglomeration problem of the hydrotalcite can be effectively avoided, and after the hydrotalcite is doped with the inorganic magnetic particles, 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
A fuel cell is a direct energy conversion device, which mainly comprises two parts, one is an energy source (such as natural gas, hydrogen, ethanol, methanol, formic acid or phosphoric acid, etc.), and the other is an oxidant (such as air or oxygen, etc.), and the device can directly convert the chemical energy generated by oxidizing fuel into electric energy, and has high energy conversion efficiency, low pollution and low noise, which is one of the most promising technologies for generating electricity by using renewable chemical energy. Among various fuel cells, the pem fuel cell has been studied most widely, but its acidic working environment makes the cell capable of using only noble metals such as platinum catalyst, resulting in a great increase in cell cost. Attention has been turned back 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 reduces manufacturing costs and, in addition, are more stable in alkaline media than in acidic media, providing a solution to the high cost and durability of catalysts. As a key component of fuel cells, anion exchange membranes are both conductors of hydroxyl ions and barriers to separation of fuel from oxidant. An ideal anion exchange membrane should have high ionic conductivity, excellent mechanical properties, sufficient chemical stability and dimensional stability.
Quaternary ammonium cationization is the obtainment of OH from polymers - One of the major pathways for conductivity. Basic anion exchange membranes with arylene as the backbone have been studied more extensively in the last decade, wherein polyphenylene oxide (PPO) is an engineering plastic with good mechanical properties and chemical stability, which can be quaternized by bromination or chloroacetylation, avoiding the need for strong carcinogenic chloromethylation reagents (such as chloromethyl ether) for other aromatic polymers, suitable for large-scale production, and PPO has been shown to have better chemical stability under strongly alkaline conditions than other polyaryl ethers (such as polyarylethersulfones), thus drawing extensive attention from researchers and industries. However, due to OH - The migration rate of (2) is lower (compared with proton), so that the anion exchange membrane can obtain high ion conductivity only at higher Ion Exchange Capacity (IEC), and the membrane is strongly water-absorbing and swelling due to too high IEC, so that the mechanical property of the membrane is greatly reduced, and the use requirement of the battery is difficult to meet. Organic-inorganic compounding is a simple and effective way to improve the overall performance of anion exchange membranes. 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 the brucite-like layer in an ordered and uniform manner, the anions are present in the layer to maintain charge conservation, and in addition, the large number of hydroxyl groups present on the surface of the LDH nanotubes help to bind more water molecules, which provides a large hydrogen bonding network through which hydrogen bonds can be rapidly broken/heavyGroup processes to facilitate the transport of OH-. Tadanaga et al [ Advanced Materials,2010,22 - And the hydrotalcite prepared by the traditional coprecipitation method and other methods is easy to agglomerate due to strong intermolecular force, so that the ion transmission capability of the hydrotalcite is greatly reduced. At present, several methods have been tried to avoid the agglomeration problem of hydrotalcite during synthesis and incorporation into polymer matrix, zhang et al [ Solid state sciences,2009,11 (9): 1597-1601 ] coating hydrotalcite on nano magnesium ferrite (MgFe) by coprecipitation method 2 O 4 ) In the above, the surface of the synthesized sample has a layered structure and also has certain magnetism, and on the basis, the synthesized sample also provides a core-shell structure model preliminarily. The hydrotalcite grows vertically and uniformly on the surface of a micron or nanometer substrate, so that the problem of difficult dispersion of the hydrotalcite can be solved, and a multi-scale and ordered multi-level structure hydrotalcite composite material can be constructed, active sites of the hydrotalcite composite material are fully exposed, and the anion conduction characteristic of the hydrotalcite composite material is exerted. In addition, a cross-linked 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 size 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-level structure hydrotalcite in the composite membrane to induce the formation of the directional ordered ion transmission channel in the membrane, thereby further improving the ion conductivity of the anion exchange membrane, remains a difficult problem to be solved urgently.
Disclosure of Invention
In view of 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 higher (normal temperature and 80 ℃) ionic conductivity, and has more excellent chemical stability (taking out the conductivity of the membrane after being soaked in a 60 ℃ 1mol/LKOH aqueous solution for 300 hours as an evaluation index) and mechanical performance.
A method for preparing a magnetic field-induced organic-inorganic composite cross-linked anion-exchange membrane, comprising the steps of:
(1) Preparing hydrotalcite coated ferroferric oxide nanoparticles: moving a glycol solution of sodium acetate trihydrate and ferric trichloride hexahydrate into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 6-12h at the temperature of 150-220 ℃, separating magnetic mud by using a magnet after the reaction kettle is cooled to the room temperature, 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 less than 100 nm; dispersing the nano ferroferric oxide particles in a mixed solvent of methanol and water with the volume ratio of 1:1-1:5 through ultrasound to form a dispersion liquid with the concentration of 0.1wt.% to 0.5wt.%, dropwise adding a mixed alkali solution into the dispersion liquid until the pH value of the dispersion liquid is 10-11, dropwise adding the mixed alkali solution and a magnesium salt-aluminum salt mixed solution together at a speed of three seconds for one drop, maintaining the pH value of the solution to be 10-11 during dropwise adding, reacting at 30-60 ℃ for 12-36 hours after dropwise adding is finished, cooling, separating out magnetic insoluble substances through magnetism, cleaning the magnetic insoluble substances with deionized water and absolute ethyl alcohol, drying and grinding to obtain hydrotalcite-coated nano ferroferric oxide particles;
further, step (1) contains CH 3 COO - 、Fe 3+ In glycol solution of (3) 3+ The molar concentration of the Fe is 0.003 to 0.007mol/L, and the Fe 3+ And CH 3 COO - The molar ratio of 1:3-1:8; the solvent in the mixed alkali solution is the same as the solvent in the magnesium salt-aluminum salt mixed solution and the solvent in the ferroferric oxide dispersion liquid, and the solvents are mixed solvents of methanol and water with 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 1:1-1:4; mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in the mixed solvent to form a magnesium salt-aluminum salt mixed solution, wherein Mg 2+ Has a molar concentration of 0.1 to 0.3mol/L, al 3+ With Mg 2+ In a molar ratio of1:1～1:3，Fe 3 O 4 With Mg 2 + In a molar ratio of 1 2+ With OH - 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 any one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
(3) Dissolving quaternized polyphenyl ether in a solvent to form a quaternized polyphenyl ether solution with the concentration of 5-30 wt.%;
further, the quaternization substitution degree of the quaternization polyphenyl ether is 20 to 60 percent, and preferably, the quaternization substitution degree of the quaternization polyphenyl ether is 35 to 55 percent; more preferably, the quaternized polyphenylene ether has a degree of quaternization 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 that used for dispersing the hydrotalcite-coated ferroferric oxide nanoparticles in the step (2).
(4) Adding glutaraldehyde into 3.5wt.% of dimethyl sulfoxide solution of polyvinyl alcohol to form a polyvinyl alcohol mixed solution, wherein the mass ratio of the glutaraldehyde to the polyvinyl alcohol is 1:5-1; then adding the polyvinyl alcohol mixed solution into the quaternized polyphenylene ether solution obtained in the step (3), and uniformly mixing to obtain a quaternized polymer mixed solution, wherein the mass ratio of polyvinyl alcohol to quaternized polymer is (1-10);
(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 polyphenylene oxide is 1;
(6) And (3) uniformly pouring the casting film dispersion liquid obtained in the step (5) onto a glass plate, applying a magnetic field with the magnetic field intensity of 0.1-0.5T vertical to the substrate to the glass plate, naturally drying the glass plate for 6-12h at room temperature, removing the magnetic field, placing the glass plate in an oven at 80 ℃ for continuously drying for 6-12h, cooling the glass plate to room temperature, uncovering the film, and carrying out anion exchange by using KOH solution to obtain the magnetic field induced organic-inorganic composite crosslinked anion exchange membrane.
Further, in the step (6), the anion exchange step is: and soaking the membrane 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.
The organic-inorganic composite cross-linked anion-exchange membrane prepared by the preparation method is applied to the preparation of the alkaline polyelectrolyte fuel cell.
Compared with the prior art, the technical scheme of the invention has the following advantages and beneficial technical effects:
1. compared with the hydrotalcite prepared by the methods of stripping/self-assembly and the like, which is very easy to agglomerate into blocks, the method takes the nano ferroferric oxide as a hydrotalcite growth substrate (shown in an attached figure 1), and controls the reaction time and the concentration of a salt solution to ensure that the hydrotalcite vertically and alternately grows on the surfaces of nano ferroferric oxide particles in an oriented manner to form a honeycomb-shaped appearance (shown in an attached figure 2), so that the hydrotalcite with high specific surface area and high active sites is obtained, and the stacking and agglomeration of the hydrotalcite are effectively prevented.
2. Compared with the conventional organic-inorganic composite mode, the casting solution is spread on the glass substrate and then placed in a magnetic field for magnetic field induction, so that the inorganic magnetic particles are directionally and regularly arranged, the agglomeration problem can be greatly reduced, the inorganic particles can form a longer-range ordered ion channel, and the ion conductivity is further improved.
3. Compared with the direct film formation of common quaternized polyphenyl ether, the method disclosed by the invention has the advantages that the quaternized polyphenyl ether and a small amount of polyvinyl alcohol mixed solution are blended to form a film, the polyvinyl alcohol has good toughness due to the long alkyl chain structure, a large amount of hydroxyl groups in the structure can provide sites for crosslinking with glutaraldehyde, the mechanical properties (strength and toughness) and the chemical stability of a composite system are enhanced, and more hydroxide radical transfer channels can be constructed for a composite crosslinked anion exchange membrane.
In conclusion, the magnetic field induced organic-inorganic composite cross-linked anion-exchange membrane containing the multilevel 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 nano ferroferric oxide in example 1.
Fig. 2 is a transmission electron microscope image of the morphology of the hydrotalcite coated nano ferroferric oxide prepared in example 1.
Fig. 3 is an XRD chart of the hydrotalcite coated nano ferroferric oxide prepared in example 1.
FIG. 4 is a scanning electron microscope cross-sectional view of the organic-inorganic composite crosslinked basic anion-exchange membrane prepared in example 1.
Detailed Description
The applicant further describes the technical solutions of the present invention with reference to the specific examples and the drawings, but the scope of the claimed invention is not limited to these embodiments.
In the following examples, "room temperature" refers to the ambient temperature of the laboratory without heating or cooling equipment, and specifically: 20-25 ℃.
Embodiment 1 a method for preparing a magnetic field-induced organic-inorganic composite cross-linked anion-exchange membrane, comprising the steps of:
(1) Dissolving sodium acetate trihydrate and ferric chloride hexahydrate in ethylene glycol to form a solution containing CH 3 COO - 、Fe 3+ The mixed salt solution is moved into a hydrothermal reaction kettle, hydrothermal reaction is carried out for 8 hours at the temperature of 200 ℃, magnetic mud is separated by a magnet after the reaction kettle is cooled to the room temperature, the magnetic mud is cleaned by deionized water and absolute ethyl alcohol, and then dried and ground to obtain nano ferroferric oxide particles, wherein a scanning electron microscope picture of the nano ferroferric oxide particles is shown in figure 1; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water with the volume ratio of 1:1 by ultrasonic to form a mixed dispersion liquid with the mass percent concentration of 0.3 percent, and adding NaOH and Na 2 CO 3 Dissolved in aqueous methanol solution (methanol)The volume ratio of the water to the water is 1:1) to form a catalyst containing OH - With CO 3 2- Mixing with alkaline solution to remove Mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in methanol water solution (methanol-water volume ratio of 1:1) to form Mg-containing solution 2+ And Al 3+ The mixed salt solution of (1). First direction Fe 3 O 4 Dropwise adding a mixed alkali solution into the particle dispersion liquid until the pH value of the dispersion liquid is 10-11, then simultaneously dropwise adding the mixed alkali solution and the magnesium salt-aluminum salt mixed solution at a dropping speed of three seconds for one drop, maintaining the pH value of the solution at 10-11 during dropwise adding, reacting for 24 hours at 30 ℃, after the reaction is finished, magnetically separating out magnetic insoluble substances, cleaning the magnetic insoluble substances with deionized water and absolute ethyl alcohol, drying and grinding to obtain hydrotalcite-coated nano ferroferric oxide particles, and marking the particles as Fe 3 O 4 @ LDH, transmission electron micrograph of which is shown in FIG. 2, XRD micrograph of which is shown in FIG. 3;
fe in the mixed glycol solution 3+ Has a molar concentration of 0.005mol/L and Fe 3+ And CH 3 COO - Is 1:5. The solvent used by the mixed alkali solution and the magnesium salt-aluminum salt mixed solution is the same as the ferroferric oxide dispersion liquid, and OH in the mixed alkali solution - The molar concentration is 0.3mol/L, OH - With CO 3 2- Is 1:3. Mg in magnesium salt-aluminum salt mixed solution 2+ Has a molar concentration of 0.1mol/L, al 3+ With Mg 2+ In a molar ratio of 1 3 O 4 With Mg 2+ 1, 6,Mg 2+ With OH - Is 1:4.
(2) Fe obtained in the step (1) 3 O 4 @ LDH was dispersed in N-methylpyrrolidone to prepare a dispersion having a concentration of 1g/20 mL.
(3) Quaternised polyphenylene oxide (polyphenylene oxide as raw material is available from Nantong star synthetic materials Co., ltd., trade name LXR045, molecular weight M) W =40000. The preparation process of the quaternized polyphenyl ether comprises the following steps: adding 10g of dried PPO and 100mL of chlorobenzene into a 250mL three-neck flask, introducing nitrogen, magnetically stirring at 80 ℃ until the PPO is completely dissolved, cooling to room temperature, adding 12g N-bromosuccinimide as a bromination test0.8g of dibenzoyl peroxide as an initiator, and the mixture is condensed and refluxed 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 ether, dissolving the brominated polyphenylene ether in 100 mLN-methyl pyrrolidone, adding 1.96g1, 2-dimethyl imidazole as quaternizing agent, reacting at 60 deg.C for 24 hr, adding the mixed solution dropwise into acetone, filtering to obtain insoluble substance, oven drying to obtain quaternized polyphenylene ether, and measuring Br by nuclear magnetic hydrogen spectrum resonance method - The content further determines that the quaternization substitution degree is 41%) is dissolved in N-methyl pyrrolidone to obtain quaternization polyphenyl ether solution with the mass percentage concentration of 9%;
(4) mu.L of 25wt.% glutaraldehyde aqueous solution was added to 1.25mL of 3.5% polyvinyl alcohol (raw material purchased from Chemicals, inc., national pharmaceutical Co., ltd., average degree of polymerization 1750. + -. 50, pH 5-7 (50 g/L, H) 2 O,25 deg.C, melting point 160-240 deg.C, density rho (20 deg.C) =0.4-0.6g/mL, flash point>And (3) forming a polyvinyl alcohol mixed solution in a dimethyl sulfoxide solution at 113 ℃, 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 polyvinyl alcohol to quaternized polyphenyl ether is 1:20; then the Fe prepared in the step (2) is put into 3 O 4 Adding the @ LDH dispersion liquid into a quaternized polymer mixed solution, adjusting the pH to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain a uniform cast film dispersion liquid, wherein the mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenylene ether is 1;
(5) And (3) pouring the casting film dispersion liquid obtained in the step (4) on a glass plate uniformly, applying a magnetic field with the magnetic field intensity of 0.4T vertical to the substrate to the glass plate, naturally drying the glass plate for 6h at room temperature, then removing the magnetic field, putting the glass plate into an oven at 80 ℃ for continuously drying for 8h, cooling the glass plate to the room temperature, uncovering the film, and finally soaking the film in a 1mol/LKOH solution for sufficient anion exchange (24 h) to obtain the organic-inorganic composite cross-linked anion exchange film induced by the magnetic field, which is abbreviated as an organic-inorganic composite cross-linked alkaline anion exchange film (film 1), wherein the cross-section of the film is shown in a scanning electron microscope (chart) in figure 4.
To carry outIn contrast, 1g of quaternized polyphenylene ether is dissolved in N-methylpyrrolidone to obtain a quaternized polyphenylene ether solution with the mass percentage concentration of 9%, and then 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 mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenylene oxide is 1.
For comparison, 1g of quaternized polyphenylene ether is dissolved in N-methylpyrrolidone to obtain a quaternized polyphenylene ether solution with the mass percentage concentration of 9%, 20 μ L of 25wt.% glutaraldehyde aqueous solution is added into 1.25mL of polyvinyl alcohol dimethyl sulfoxide solution with the mass percentage concentration of 3.5% to form a polyvinyl alcohol mixed solution, then the polyvinyl alcohol mixed solution is added into the quaternized polyphenylene ether solution, and a quaternized polymer mixed solution is obtained after uniform mixing, wherein the mass ratio of polyvinyl alcohol to quaternized polymer is 1:20; adjusting the pH value to 4 by hydrochloric acid, fully stirring and mixing to obtain uniform casting film dispersion liquid, uniformly pouring the casting film dispersion liquid on a glass plate, naturally drying for 6h at room temperature, removing a magnetic field, putting the casting film dispersion liquid in an oven at 80 ℃ for continuously drying for 8h, cooling to room temperature, uncovering the film, finally soaking the film in 1mol/L KOH solution for full anion exchange (24 h), and obtaining a blended crosslinked anion exchange membrane (abbreviated as a crosslinked alkaline anion exchange membrane (membrane 1-2)).
The performance test results 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 the above example 1 are shown in table 1:
TABLE 1
As can be seen from the results in table 1, the ion conductivity of the organic-inorganic composite crosslinked basic anion-exchange membrane (membrane 1) prepared in example 1 at 80 ℃ is improved by 121% compared with that of the crosslinked basic anion-exchange membrane (membrane 1-2), and meanwhile, 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 composite membrane shows a remarkable synergistic enhancement effect of the inorganic substance (hydrotalcite-coated nano ferroferric oxide) and the blended and crosslinked polyvinyl alcohol, and the stability of the composite membrane in an alkaline solution is greatly improved. Although the tensile strength, elongation at break and alkaline stability of the cross-linked 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 cross-linked alkaline anion exchange membrane is difficult to meet the use requirements of fuel cells.
As can be seen from the scanning electron microscope image of the appearance of the nano ferroferric oxide shown in FIG. 1, the nano ferroferric oxide particles have uniform thickness distribution, the particle size is about 100nm, and no obvious coating substance exists on the surface; as can be seen from the transmission electron microscope image of the appearance of the hydrotalcite coated nano ferroferric oxide in FIG. 2, a multi-scale composite material of the two-dimensional layered flaky hydrotalcite coated nano ferroferric oxide is formed, and the particle diameter is about 200nm; as can be seen from the XRD pattern of the hydrotalcite coated nano ferroferric oxide in fig. 3, characteristic diffraction peaks of hydrotalcite and ferroferric oxide appear at the same time, and comparison with the standard patterns of ferroferric oxide and magnesium-aluminum hydrotalcite shows that the magnesium-aluminum hydrotalcite can be generated in situ by the method; as can be seen from the cross-sectional scanning electron microscope image of the organic-inorganic composite cross-linked basic anion-exchange membrane in fig. 4, the cross section of the composite membrane is very compact, and a long-chain structure formed by inorganic nanoparticles can be observed, which indicates that the inorganic nanoparticles not only have good dispersibility in the polymer matrix, but also are directionally arranged (in the arrow direction in fig. 4) under the action of a magnetic field, and the compact structure is beneficial to improving the mechanical properties and ionic conductivity of the composite membrane.
Embodiment 2 a method for preparing a magnetic field-induced organic-inorganic composite crosslinked anion exchange membrane, comprising the steps of:
(1) Dissolving sodium acetate trihydrate and ferric chloride hexahydrate in ethylene glycol to form a solution containing CH 3 COO - 、Fe 3 + The salt solution is moved into a hydrothermal reaction kettle, hydrothermal reaction is carried out for 12 hours at the temperature of 150 ℃, magnetic mud is separated by a magnet after the reaction kettle is cooled to the room temperature, the magnetic mud is cleaned by deionized water and absolute ethyl alcohol, and then the magnetic mud is dried and ground to obtain nano ferroferric oxide particles; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water with the volume ratio of 1:5 by ultrasonic to form a mixed dispersion liquid with the mass percent concentration of 0.1 percent, and adding NaOH and Na 2 CO 3 Dissolving in aqueous methanol to form a solution containing OH - With CO 3 2- Mixing with alkaline solution to remove Mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in methanol water solution to form Mg-containing solution 2+ And Al 3+ Mixed salt solution of (2), first to Fe 3 O 4 Dropwise adding a mixed alkali solution into the particle dispersion liquid until the pH value of the dispersion liquid is 10-11, then dropwise adding the mixed alkali solution and the magnesium salt-aluminum salt mixed solution together at the dropping speed of three seconds, dropwise adding the solution, maintaining the pH value of the solution at 10-11 during dropwise adding, reacting for 12 hours at 60 ℃, after the reaction is finished, magnetically separating out magnetic insoluble substances, cleaning the magnetic insoluble substances with deionized water and absolute ethyl alcohol, drying and grinding to obtain the hydrotalcite-coated nano ferroferric oxide (Fe) 3 O 4 @ LDH) particles.
Fe in the mixed glycol solution 3+ Has a molar concentration of 0.003mol/L, fe 3+ And CH 3 COO - The molar ratio of the mixed alkali solution to the magnesium salt-aluminum salt mixed solution is 1:8, the solvent used by the mixed alkali solution and the magnesium salt-aluminum salt mixed solution is the same as the ferroferric oxide dispersion liquid, and OH in the mixed alkali solution - The molar concentration is 0.2mol/L, OH - With CO 3 2- Is 1:4. Mg in magnesium salt-aluminum salt mixed solution 2+ Has a molar concentration of 0.1mol/L, al 3+ With Mg 2+ In a molar ratio of 1 3 O 4 With Mg 2+ In a molar ratio of 1 2+ With OH - Is 1:4.
(2) Fe obtained in the step (1) 3 O 4 @ LDH was dispersed in N, N-dimethylformamide to prepare a dispersion having a concentration of 1g/20 mL.
(3) Quaternised polyphenylene oxide (polyphenylene oxide as raw material is available from Nantong star synthetic materials Co., ltd., trade name LXR045, molecular weight M) W =40000. The preparation process of the quaternized polyphenyl ether comprises the following steps: adding 10g of dried PPO and 100mL of chlorobenzene into a 250mL three-neck flask, introducing nitrogen, magnetically stirring at 80 ℃ until the PPO is completely dissolved, cooling to room temperature, adding 12g N-bromosuccinimide as a bromination reagent, 0.8g of dibenzoyl peroxide as an initiator, and introducing nitrogen to perform condensation reflux reaction at 80 ℃ for 3 hours. Cooling to room temperature, precipitating with anhydrous methanol, filtering, washing, drying to obtain brominated polyphenylene ether, dissolving the brominated polyphenylene ether in 100 mLN-methyl pyrrolidone, adding 1.96g1, 2-dimethyl imidazole as quaternizing agent, reacting at 60 deg.C for 24 hr, adding the mixed solution dropwise into acetone, filtering to obtain insoluble substance, oven drying to obtain quaternized polyphenylene ether, and measuring Br by nuclear magnetic hydrogen spectrum resonance method - The content further determines that the quaternization substitution degree is 41%) is dissolved in N, N-dimethylformamide to obtain a quaternization polyphenyl ether solution with the mass percentage concentration of 9%;
(4) Adding 20 mu L of 25wt.% glutaraldehyde aqueous solution into 0.8mL of 3.5% polyvinyl alcohol dimethyl sulfoxide solution to form a polyvinyl alcohol mixed solution, adding the polyvinyl alcohol mixed solution into the quaternized polyphenylene ether solution obtained in the step (3), and uniformly mixing to obtain a quaternized polymer mixed solution, wherein the mass ratio of polyvinyl alcohol to quaternized polyphenylene ether is 1:20; then the Fe prepared in the step (2) 3 O 4 Adding the @ LDH dispersion liquid into a quaternized polymer mixed solution, adjusting the pH to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain a uniform cast film dispersion liquid, wherein the mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenylene oxide is 1;
(5) And (3) uniformly pouring the casting film dispersion liquid obtained in the step (4) on a glass plate, applying a magnetic field with the magnetic field intensity of 0.2T vertical to the substrate to the glass plate, naturally drying for 6h at room temperature, then removing the magnetic field, putting the glass plate into an oven with the temperature of 80 ℃, continuously drying for 8h, cooling to room temperature, then uncovering the film, finally soaking the film in 1mol/LKOH solution for sufficient anion exchange (24 h), and obtaining the organic-inorganic composite cross-linked anion exchange film induced by the magnetic field, which is abbreviated as an organic-inorganic composite cross-linked alkaline anion exchange film.
Embodiment 3 a method for preparing a magnetic field-induced organic-inorganic composite crosslinked anion exchange membrane, comprising the steps of:
(1) Dissolving sodium acetate trihydrate and ferric chloride hexahydrate in ethylene glycol to form a solution containing CH 3 COO - 、Fe 3 + The salt solution is moved into a hydrothermal reaction kettle, hydrothermal reaction is carried out for 9 hours at 180 ℃, magnetic mud is separated by a magnet after the reaction kettle is cooled to room temperature, the magnetic mud is cleaned by deionized water and absolute ethyl alcohol, and then the magnetic mud is dried and ground to obtain nano ferroferric oxide particles; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water with the volume ratio of 1:2 by ultrasonic to form a mixed dispersion liquid with the mass percent concentration of 0.4 percent, and adding NaOH and Na 2 CO 3 Dissolving in aqueous methanol to form a solution containing OH - With CO 3 2- Mixing with alkaline solution to remove Mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in methanol water solution to form Mg-containing solution 2+ And Al 3+ The mixed salt solution of (1). First direction Fe 3 O 4 Dropping a mixed alkali solution into the particle dispersion until the pH value of the dispersion is 10-11, then dropping the mixed alkali solution and the magnesium salt-aluminum salt mixed solution together at the dropping speed of three seconds for one drop, maintaining the pH value of the solution at 10-11 during the dropping, reacting for 36 hours at 45 ℃, after the reaction is finished, magnetically separating out magnetic insoluble substances, cleaning the magnetic insoluble substances by using deionized water and absolute ethyl alcohol, drying and grinding to obtain the hydrotalcite-coated nano ferroferric oxide particles.
Fe in the mixed glycol solution 3+ Has a molar concentration of 0.004mol/L, fe 3+ And CH 3 COO - Is 1:3. The mixed alkali solution and the magnesium salt-aluminum salt mixed solution use the same solvent as the ferroferric oxide dispersion liquid, and OH in the mixed alkali solution - The molar concentration is 0.04mol/L, OH - With CO 3 2- Is 1:2. Mg in magnesium salt-aluminum salt mixed solution 2+ Has a molar concentration of 0.15mol/L and Al 3+ With Mg 2+ 1, 3, fe 3 O 4 With Mg (NO) 3 ) 2 ·6H 2 Molar ratio of O1 2+ With OH - Is 1:4.
(2) Fe obtained in the step (1) 3 O 4 @ LDH was dispersed in N, N-dimethylacetamide to prepare a 1g/20mL dispersion.
(3) Quaternised polyphenylene oxide (the raw material polyphenylene oxide was obtained from Nantong star synthetic materials Co., ltd., trade name LXR045, molecular weight M) W =40000. The preparation process of the quaternized polyphenyl ether comprises the following steps: adding 10g of dried PPO and 100mL of chlorobenzene into a 250mL three-neck flask, introducing nitrogen, magnetically stirring at 80 ℃ until the PPO is completely dissolved, cooling to room temperature, adding 12g N-bromosuccinimide as a bromination reagent, 0.8g of dibenzoyl peroxide as an initiator, and introducing nitrogen to perform condensation reflux reaction at 80 ℃ for 3 hours. Cooling to room temperature, precipitating with anhydrous methanol, filtering, washing, drying to obtain brominated polyphenylene oxide, dissolving the brominated polyphenylene oxide in 100ml LN-methyl pyrrolidone, adding 1.96g1, 2-dimethyl imidazole as quaternization reagent, reacting at 60 deg.C for 24 hr, adding the mixed solution dropwise into acetone, filtering to obtain insoluble substance, oven drying to obtain quaternized polyphenylene oxide, and measuring Br by nuclear magnetic resonance spectroscopy - The content further determines that the quaternization substitution degree is 41%) is dissolved in N, N-dimethylacetamide to obtain a quaternization polyphenyl ether solution with the mass percentage concentration of 9%;
(4) Adding 20 mu L of 25wt.% glutaraldehyde aqueous solution into 2.5mL of 3.5 mass percent polyvinyl alcohol dimethyl sulfoxide solution to form polyvinyl alcohol mixed solution, adding the polyvinyl alcohol mixed solution into the quaternized polyphenylene ether solution obtained in the step (3), and uniformly mixing to obtain quaternized polymer mixed solution, wherein the polyvinyl alcohol mixed solution isThe mass ratio of the quaternary ammonium compound to the quaternary ammonium polyphenyl ether is 1:20; then the Fe prepared in the step (2) 3 O 4 Adding the @ LDH dispersion liquid into a quaternary ammonium polymer mixed 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 mass ratio of added hydrotalcite coated ferroferric oxide to quaternary ammonium polyphenyl ether is 1;
(5) And (3) uniformly pouring the casting film dispersion liquid obtained in the step (4) on a glass plate, applying a magnetic field with the magnetic field intensity of 0.4T vertical to the substrate to the glass plate, naturally drying the glass plate for 6h at room temperature, then placing the glass plate into an oven with the temperature of 80 ℃ for continuously drying for 8h, cooling the glass plate to the room temperature, then uncovering the film, finally soaking the film in 1mol/LKOH solution for sufficient anion exchange (24 h), and obtaining the organic-inorganic composite cross-linked anion exchange membrane induced by the magnetic field, which is abbreviated as an organic-inorganic composite cross-linked alkaline anion exchange membrane.
Embodiment 4 a method for preparing a magnetic field-induced organic-inorganic composite crosslinked anion exchange membrane, comprising the steps of:
(1) Dissolving sodium acetate trihydrate and ferric chloride hexahydrate in ethylene glycol to form a solution containing CH 3 COO - 、Fe 3 + The mixed salt solution is moved into a hydrothermal reaction kettle, hydrothermal reaction is carried out for 12 hours at the temperature of 200 ℃, magnetic mud is separated by a magnet after the reaction kettle is cooled to the room temperature, the magnetic mud is cleaned by deionized water and absolute ethyl alcohol, and then the magnetic mud is dried and ground to obtain nano ferroferric oxide particles; dispersing nano ferroferric oxide particles in a mixed solvent of methanol and water with the volume ratio of 3:7 by ultrasonic to form a mixed dispersion liquid with the mass percent concentration of 0.5 percent, and adding NaOH and Na 2 CO 3 Dissolved in aqueous methanol to form a solution containing OH - With CO 3 2- Mixing with alkaline solution to remove Mg (NO) 3 ) 2 ·6H 2 O and Al (NO) 3 ) 3 ·9H 2 Dissolving O in deionized water to form a solution containing Mg 2+ And Al 3+ The mixed salt solution of (1). First oriented Fe 3 O 4 Dropping mixed alkali solution into the particle dispersion until the pH value of the dispersion is 10-11, and then dropping the mixed alkali solution and the magnesium salt-aluminum salt mixed solution together at the dropping speed of threeAnd (3) dropping a drop of solution in seconds, maintaining the pH value of the solution at 10-11 during the dropping, reacting for 18 hours at 50 ℃, after the reaction is finished, magnetically separating out magnetic insoluble substances, cleaning the magnetic insoluble substances by using deionized water and absolute ethyl alcohol, drying and grinding to obtain the hydrotalcite-coated nano ferroferric oxide particles.
Fe in the mixed glycol solution 3+ Has a molar concentration of 0.007mol/L, fe 3+ And CH 3 COO - Is 1:7. The solvent used by the mixed alkali solution and the magnesium salt-aluminum salt mixed solution is the same as the ferroferric oxide dispersion liquid, and OH in the mixed alkali solution - The molar concentration is 0.04mol/L, OH - With CO 3 2- Is 1:2. Mg in magnesium salt-aluminum salt mixed solution 2+ Has a molar concentration of 0.25mol/L, al 3+ With Mg 2+ In a molar ratio of 1 3 O 4 With Mg (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1 2+ With OH - Is 1:4.
(2) Fe obtained in the step (1) 3 O 4 @ LDH was dispersed in dimethyl sulfoxide to prepare a dispersion having a concentration of 1g/20 mL.
(3) Quaternised polyphenylene oxide (the raw material polyphenylene oxide was obtained from Nantong star synthetic materials Co., ltd., trade name LXR045, molecular weight M) W =40000. The preparation process of the quaternized polyphenyl ether comprises the following steps: adding 10g of dried PPO and 100mL of chlorobenzene into a 250mL three-neck flask, introducing nitrogen, magnetically stirring at 80 ℃ until the PPO is completely dissolved, cooling to room temperature, adding 12g N-bromosuccinimide as a bromination reagent, 0.8g of dibenzoyl peroxide as an initiator, and introducing nitrogen to perform condensation reflux reaction at 80 ℃ for 3 hours. Cooling to room temperature, precipitating with anhydrous methanol, filtering, washing, drying to obtain brominated polyphenylene oxide, dissolving the brominated polyphenylene oxide in 100ml LN-methyl pyrrolidone, adding 2.61g 1, 2-dimethyl imidazole as quaternization reagent, reacting at 60 deg.C for 24 hr, adding the mixed solution dropwise into acetone, filtering to obtain insoluble substance, oven drying to obtain quaternized polyphenylene oxide, and measuring Br by nuclear magnetic resonance spectroscopy - The content further determines that the quaternization substitution degree is 55%) is dissolved in dimethyl sulfoxide to obtain the mass percent concentrationA 9% solution of quaternized polyphenylene ether;
(4) Adding 20 mu L of 25wt.% glutaraldehyde aqueous solution into 1.25mL of 3.5% polyvinyl alcohol dimethyl sulfoxide solution to form polyvinyl alcohol mixed solution, adding the polyvinyl alcohol mixed solution into the quaternized polyphenylene ether solution obtained in the step (3), and uniformly mixing to obtain quaternized polymer mixed solution, wherein the mass ratio of polyvinyl alcohol to quaternized polyphenylene ether is 1:20; then the Fe prepared in the step (2) is put into 3 O 4 Adding the @ LDH dispersion liquid into a quaternized polymer mixed solution, adjusting the pH to 4 by hydrochloric acid, fully mixing and performing ultrasonic dispersion to obtain a uniform cast film dispersion liquid, wherein the mass ratio of the added hydrotalcite coated ferroferric oxide to the quaternized polyphenylene oxide is 1;
(5) And (3) uniformly pouring the casting film dispersion liquid obtained in the step (4) on a glass plate, applying a magnetic field with the magnetic field intensity of 0.4T vertical to the substrate to the glass plate, naturally drying the glass plate for 6h at room temperature, then placing the glass plate into an oven with the temperature of 80 ℃ for continuously drying for 8h, cooling the glass plate to the room temperature, then uncovering the film, finally soaking the film in 1mol/LKOH solution for sufficient anion exchange (24 h), and obtaining the organic-inorganic composite cross-linked anion exchange membrane induced by the magnetic field, which is abbreviated as an organic-inorganic composite cross-linked alkaline anion exchange membrane.
Table 2 shows the performance index data of the organic-inorganic composite crosslinking alkaline anion-exchange membranes prepared in the examples 2-4. As can be seen from the data in the table, the ion conductivity of the composite alkaline anion-exchange membrane at 80 ℃ is more than or equal to 45mS cm -1 After the membrane is soaked in 1mol/L KOH aqueous solution 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 high level (more than or equal to 35 MPa). Example 4 in the preparation of organic-inorganic composite alkaline anion-exchange membranes, the quaternization substitution degree of the used quaternization polymer solution is as high as 55%, and the prepared polyelectrolyte membranes have high ionic conductivity (more than or equal to 70mS cm) -1 ) But the tensile strength and alkaline stability are slightly inferior.
TABLE 2
The film property test conditions prepared in the above examples are uniformly described as follows:
(1) Ionic conductivity: the resistance of the film was tested on a frequency response analyzer with a frequency sweep range of 1-10 6 Hz, and the amplitude of the alternating current signal is 50mV. 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 was calculated by the following formula:
in the formula, L and A are the distance between two electrodes and the effective cross-sectional area of the film to be tested between the two electrodes respectively, R is the resistance of the film, and the Nyquist diagram obtained by the alternating current impedance test is obtained.
(2) Tensile strength, elongation at break: the film was cut into a rectangular specimen having a length of 40mm and a width of 10mm, and the specimen was tested on an electronic tensile machine at a tensile speed of 1 mm/min.
(3) Alkaline stability: and (3) soaking the cut alkaline membrane (with the length multiplied by the width =3cm multiplied by 2 cm) in 1mol/LKOH aqueous solution at 60 ℃ for 300h, taking out, repeatedly washing with deionized water until the washing liquid is neutral, then measuring the ionic conductivity of the composite membrane at 80 ℃, and recording the residual ionic conductivity.
Claims (8)
1. A preparation method of a magnetic field induced organic-inorganic composite cross-linked anion exchange membrane is characterized by comprising the following steps:
(1) Preparing hydrotalcite coated ferroferric oxide nanoparticles: moving a 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 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; then dispersing the nano ferroferric oxide particles in a mixed solvent of methanol and water with the volume ratio of 1: 1~1: 5 through ultrasound to form a dispersion liquid with the concentration of 0.1 wt% -0.5 wt%, firstly dropwise adding a mixed alkali solution into the dispersion liquid until the pH value of the dispersion liquid is 10 to 11, then dropwise adding the mixed alkali solution and a magnesium salt-aluminum salt mixed solution together at a dropping speed of three seconds, maintaining the pH value of the solution at 10 to 11 during dropwise adding, reacting at 30 to 60 ℃ for 12 to 36h after dropwise adding is finished, cooling, magnetically separating out magnetic insoluble substances, cleaning the magnetic insoluble substances by using deionized water and absolute ethyl alcohol, 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 a 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 quaternization substitution degree of the quaternized polyphenyl ether is 20-60%;
(4) Adding glutaraldehyde into a dimethyl sulfoxide solution of polyvinyl alcohol with the concentration of 3.5 wt% to form a polyvinyl alcohol mixed solution, wherein the mass ratio of the glutaraldehyde to the polyvinyl alcohol is 1: 5~1: 20; then adding the mixed solution of polyvinyl alcohol 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 to 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 polyphenylene oxide is 1:20 to 1:100, adjusting the pH to 4 by hydrochloric acid, and fully mixing and ultrasonically dispersing 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 intensity of 0.1-0.5T vertical to the substrate to the glass plate, naturally drying the glass plate for 6-12h at room temperature, then removing the magnetic field, placing the glass plate in an oven at 80 ℃ for continuously drying for 6-12h, cooling the glass plate to the room temperature, uncovering the film, and carrying out anion exchange by using KOH solution to obtain the magnetic field induced organic-inorganic composite cross-linked anion exchange membrane.
2. The method according to claim 1, wherein the step (1) contains CH 3 COO - 、Fe 3+ In glycol solution of (3) 3+ The molar concentration of the Fe is 0.003 to 0.007mol/L, and the Fe 3+ And CH 3 COO - In a molar ratio of 1: 3~1: 8; the solvent of the mixed alkali solution and the magnesium salt-aluminum salt mixed solution is the same as that of the ferroferric oxide dispersion liquid, and the mixed alkali solution contains NaOH and Na 2 CO 3 ，OH - The molar concentration is 0.2 to 0.3mol/L, OH - With CO 3 2- In a molar ratio of 1: 1~1: 4; mg in magnesium salt-aluminum salt mixed solution 2+ The molar concentration of (b) is 0.1 to 0.3mol/L, al 3+ With Mg 2+ In a molar ratio of 1: 1~1: 3, fe 3 O 4 With Mg 2+ In a molar ratio of 1:6 2+ With OH - In a molar ratio of 1:4.
3. The production method according to claim 1 or 2, characterized in that 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. The method according to claim 3, wherein the solvent is the same in steps (2) and (3).
5. The method according to claim 1, wherein the quaternized polyphenylene ether has a degree of quaternization substitution of 35 to 55%.
6. The method according to claim 1, wherein the quaternized polyphenylene ether has a degree of quaternary substitution of 40 to 45%.
7. The method according to claim 1, wherein in the step (6), the anion exchange step is: the membrane was soaked in 1mol/L KOH solution 1-24h for anion exchange.
8. The use of an organic-inorganic composite cross-linked anion exchange membrane prepared by the preparation method of any one of claims 1~7 in the preparation of an alkaline polyelectrolyte fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210976489.0A CN115353657B (en) | 2022-08-15 | 2022-08-15 | Preparation method of magnetic field induced organic-inorganic composite cross-linked anion exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210976489.0A CN115353657B (en) | 2022-08-15 | 2022-08-15 | Preparation method of magnetic field induced organic-inorganic composite cross-linked anion exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115353657A true CN115353657A (en) | 2022-11-18 |
| CN115353657B CN115353657B (en) | 2023-07-04 |
Family
ID=84032999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210976489.0A Active CN115353657B (en) | 2022-08-15 | 2022-08-15 | Preparation method of magnetic field induced organic-inorganic composite cross-linked anion exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115353657B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101647780A (en) * | 2009-09-23 | 2010-02-17 | 北京化工大学 | Core-shell type magnetic nano-composite particle based on Fe3O4 and houghite and preparation method thereof |
| CN109078501A (en) * | 2018-07-11 | 2018-12-25 | 天津大学 | A kind of preparation method of the amberplex with orderly ion conduction structure |
| CN109818023A (en) * | 2019-01-17 | 2019-05-28 | 湖北工程学院 | Compound alkaline polyelectrolyte film of a kind of flower-shaped hydrotalcite and its preparation method and application |
| CN109904501A (en) * | 2019-01-17 | 2019-06-18 | 湖北工程学院 | Compound alkaline polyelectrolyte film of one kind and its preparation method and application |
| 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 |
-
2022
- 2022-08-15 CN CN202210976489.0A patent/CN115353657B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101647780A (en) * | 2009-09-23 | 2010-02-17 | 北京化工大学 | Core-shell type magnetic nano-composite particle based on Fe3O4 and houghite and preparation method thereof |
| CN109078501A (en) * | 2018-07-11 | 2018-12-25 | 天津大学 | A kind of preparation method of the amberplex with orderly ion conduction structure |
| CN109818023A (en) * | 2019-01-17 | 2019-05-28 | 湖北工程学院 | Compound alkaline polyelectrolyte film of a kind of flower-shaped hydrotalcite and its preparation method and application |
| CN109904501A (en) * | 2019-01-17 | 2019-06-18 | 湖北工程学院 | Compound alkaline polyelectrolyte film of one kind and its preparation method and application |
| 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)
| Title |
|---|
| NANJUN CHEN ET AL.: ""Magnetic field-oriented ferroferric oxide/poly(2,6- dimethyl-1,4-phenylene oxide) hybrid membranes for anion exchange membrane applications"", THE ROYAL SOCIETY OF CHEMISTRY, vol. 10, no. 39 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115353657B (en) | 2023-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Vinothkannan et al. | Ceria stabilized by titanium carbide as a sustainable filler in the nafion matrix improves the mechanical integrity, electrochemical durability, and hydrogen impermeability of proton-exchange membrane fuel cells: effects of the filler content | |
| Chen et al. | High-performance layered double hydroxide/poly (2, 6-dimethyl-1, 4-phenylene oxide) membrane with porous sandwich structure for anion exchange membrane fuel cell applications | |
| Salarizadeh et al. | Novel proton exchange membranes based on proton conductive sulfonated PAMPS/PSSA-TiO2 hybrid nanoparticles and sulfonated poly (ether ether ketone) for PEMFC | |
| Bano et al. | Studies on nano composites of SPEEK/ethylene glycol/cellulose nanocrystals as promising proton exchange membranes | |
| Su et al. | Synthesis and characterization of polypyrrole doped with anionic spherical polyelectrolyte brushes. | |
| Gosalawit et al. | Sulfonated montmorillonite/sulfonated poly (ether ether ketone)(SMMT/SPEEK) nanocomposite membrane for direct methanol fuel cells (DMFCs) | |
| Salarizadeh et al. | Influence of amine-functionalized iron titanate as filler for improving conductivity and electrochemical properties of SPEEK nanocomposite membranes | |
| Wang et al. | Anatase titania coated CNTs and sodium lignin sulfonate doped chitosan proton exchange membrane for DMFC application | |
| Zhang et al. | Polydopamine-modified sulfonated polyhedral oligomeric silsesquioxane: an appealing nanofiller to address the trade-off between conductivity and stabilities for proton exchange membrane | |
| Guo et al. | Stable branched polybenzimidazole high temperature proton exchange membrane: Crosslinking and pentaphosphonic-acid doping lower fuel permeability and enhanced proton transport | |
| Kumar et al. | Synergistic role of graphene oxide-magnetite nanofillers contribution on ionic conductivity and permeability for polybenzimidazole membrane electrolytes | |
| Elumalai et al. | Anion exchange composite membrane based on octa quaternary ammonium Polyhedral Oligomeric Silsesquioxane for alkaline fuel cells | |
| Hu et al. | A facile construction of quaternized polymer brush-grafted graphene modified polysulfone based composite anion exchange membranes with enhanced performance | |
| Hu et al. | Glycine betaine intercalated layered double hydroxide modified quaternized chitosan/polyvinyl alcohol composite membranes for alkaline direct methanol fuel cells | |
| Yuan et al. | Novel quaternized carbon dots modified polysulfone-based anion exchange membranes with improved performance | |
| Shi et al. | Controlling conduction environments of anion exchange membrane by functionalized SiO2 for enhanced hydroxide conductivity | |
| Zhao et al. | Enhanced performance of poly (ether sulfone) based composite proton exchange membranes with sulfonated polymer brush functionalized graphene oxide | |
| Wang et al. | Electric-field-aligned functionalized-layered double hydroxide/polyphenyl ether composite membrane for ion transport | |
| Bavasso et al. | Sulfonated Fe3O4/PES nanocomposites as efficient separators in microbial fuel cells | |
| Li et al. | Extra highways for proton diffusion in TiO2@ MIL-101-Cr/Nafion composite membranes with high single-cell performance | |
| Chu et al. | A highly stable Cu (OH) 2-poly (vinyl alcohol) nanocomposite membrane for dramatically enhanced direct borohydride fuel cell performance | |
| Nie et al. | Hierarchical Fe3O4@ LDH-incorporated composite anion exchange membranes for fuel cells based on magnetic field orientation | |
| Yuan et al. | Mussel-inspired functionalized LDH as covalent crosslinkers for constructing micro-crosslinking fluorenyl-containing polysulfone-based composite anion exchange membranes with enhanced properties | |
| Swaghatha et al. | Improved proton conductivity in MoS2–NiO–Co3O4 filled chitosan based proton exchange membranes for fuel cell applications | |
| Huang et al. | Highly cationized and porous hyper-cross-linked polymer nanospheres for composite anion exchange membranes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |