CN109755613B - Three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane and preparation method thereof - Google Patents
Three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane and preparation method thereof Download PDFInfo
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- CN109755613B CN109755613B CN201811557759.4A CN201811557759A CN109755613B CN 109755613 B CN109755613 B CN 109755613B CN 201811557759 A CN201811557759 A CN 201811557759A CN 109755613 B CN109755613 B CN 109755613B
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Abstract
The invention belongs to the technical field of fuel cells, and particularly relates to a preparation method of a three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane, which comprises the following steps: 1) dissolving the sulfonated aromatic polymer in a first solvent, and then diluting with a second solvent; 2) pouring the sulfonated aromatic polymer solution obtained in the step 1) onto a polydopamine modified three-dimensional framework, and drying to obtain the composite proton exchange membrane. The composite proton exchange membrane prepared by the invention has excellent alcohol resistance, proton conductivity and mechanical property. The composite membrane has low cost, excellent comprehensive performance and wide prospect in direct methanol fuel cells.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane and a preparation method thereof.
Background
Direct Methanol Fuel Cells (DMFCs), which are one type of Polymer Electrolyte Membrane Fuel Cells (PEMFCs), attract a wide range of attention in both academic and industrial fields because of their high energy conversion efficiency at low temperatures, and liquid methanol is easier to store and transport than hydrogen fuel. The Proton Exchange Membrane (PEM) is an important component of a DMFC, and is both the electrolyte for proton transport and the barrier separating the anode/cathode and preventing fuel permeation. Among the many proton exchange membranes developed to date, the perfluorosulfonic acid membrane (PFSA, typically
) The membrane is the dominant product of the proton exchange membrane of the commercial fuel cell due to high proton conductivity, excellent strength (about 25MPa) and flexibility (elongation at break is about 180%). However,
the excessive production and processing costs of the film pose a significant impediment to its wide-scale application. In addition, during cell operation, methanol fuel can rapidly permeate through these PFSAs, resulting in fuel waste and a significant reduction in coulombic efficiency. Much research has focused on the development of polyelectrolyte replacement PFSAs.
Among the numerous candidate materials, non-fluorinated polymers, particularly sulfonated aromatic polymers, have been extensively studied and evaluated as alternative PEMs for DMFC applications. These sulfonated aryl PEMs, such as Sulfonated Polyaryletherketones (SPEEK), Sulfonated Polyarylsulfones (SPSF), Sulfonated Polyarylethersulfones (SPES), and sulfonated polyphenylene oxides (SPPO), are cost effective, thermally stable, and chemically stable, while they also exhibit excellent fuel barrier capabilities. However, sulfonated aromatic polymers generally have some of the following deteriorated properties compared to commercially available PFSAs: sulfonated aromatic hydrocarbon-based membranes exhibit poor flexibility (less than 40% elongation at break) due to their relatively rigid aromatic hydrocarbon polymer backbone, and are not satisfactory. For practical applications of fuel cells, even if they have a satisfactory yield strength (over 20 MPa). Basically, poor toughness of the PEM not only affects its processability during Membrane Electrode Assembly (MEA) manufacture, but also tends to cause mechanical damage during long-term fuel cell operation due to fluctuations in operating temperature and humidity. Based on the above considerations, how to improve the toughness of the sulfonated aromatic hydrocarbon polymer and ensure good proton conductivity and methanol barrier property of the sulfonated aromatic hydrocarbon polymer is the key for long-term high-efficiency application of the sulfonated aromatic hydrocarbon polymer in the DMFC.
A simple and effective way to solve the above problem is to combine a polymer matrix with a flexible substrate. For example, porous polytetrafluoroethylene (ePFTE) has been used commercially as a porous substrate to make perfluorosulfonic acid Polymer (PFSA) filled ePTFE membranes. In addition, the nanofiber membrane prepared by electrospinning technology has been widely studied in recent years due to its high pore structure, ultra-high surface-to-volume ratio and controllable pore size. Electrospinning is a versatile and easily scalable technique that can be used to produce desired structures using different processing methods (e.g., coaxial and multi-needle electrospinning). The current methods of making electrospun nanofibers (PEMs) are broadly divided into two categories: one is to spin proton conducting polymer into nanofibers and then impregnate the nanofibers into a film with mechanically supported non-proton conducting polymer. However, poor spinnability of proton-conducting polymers is a non-negligible problem. Due to the low degree of polymer chain entanglement, PFSA plasma ionomers tend to be electrosprayed into beads rather than fibers, which is very detrimental to the large scale production of electrospun ionomer nanofiber PEMs. Thus, another approach to composite nanofiber membranes by electrospinning using proton conducting polymers and non-proton conducting but highly spinnable polymers is promising compared to. Among the many typical electrospinnable polymers, polyvinylidene fluoride (PVDF) and Polyacrylonitrile (PAN) electrospun nanofiber membranes have been commercially and widely used as electrolyte substrates for lithium ion batteries and fuel cells due to their good mechanical properties, high thermal stability and chemical stability. In addition, non-woven fabrics are also a support material with high toughness, high thermal stability and chemical stability. The composite membrane of the sulfonated aromatic polymer supported by the three-dimensional framework combines the advantages of two materials, and can achieve more balanced performance so as to be used as polyelectrolyte of a direct methanol fuel cell.
Disclosure of Invention
The application designs a solvent/polymer/non-solvent system in a true solution state, and the structure of the obtained composite membrane is more compact by adjusting the solubility parameter and viscosity of the solvent. Meanwhile, in order to improve interfacial bonding between the hydrophilic sulfonated aromatic polymer and the hydrophobic three-dimensional skeleton, the three-dimensional skeleton is surface-modified with dopamine. And the microstructure, the mechanical property, the methanol barrier property and the DMFC single cell property of the prepared membrane are researched and discussed in more detail.
The invention aims to provide a three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane which has high conductivity, low methanol permeation and excellent mechanical properties.
The invention also aims to provide a preparation method of the proton exchange membrane compounded by the three-dimensional framework and the sulfonated aromatic polymer.
In order to achieve the purpose, the invention adopts the following technical measures: a preparation method of a three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane comprises the following steps:
1) dissolving the sulfonated aromatic polymer in a first solvent, and then diluting with a second solvent;
2) and pouring a sulfonated aromatic polymer solution onto the polydopamine modified three-dimensional framework, and drying to obtain the composite proton exchange membrane.
Wherein, when the step 2) is carried out, the polydopamine modified three-dimensional framework is placed in a casting film groove.
The first solvent is any one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, and the concentration of the sulfonated aromatic polymer solution obtained by dissolving the first solvent is 6-10 wt%. Preferably, in a preferred embodiment of the present invention, the first solvent is N, N-dimethylacetamide, and the conductivity of the obtained composite membrane is higher. Preferably, the solution concentration is 6, 7, 8, 9, 10wt%, etc., and the solution of the sulfonated aromatic polymer having such a concentration has dilutability and film-forming property.
Wherein the second solvent is any one or a mixture of methanol, ethanol and water, and the concentration of the sulfonated aromatic polymer solution obtained by diluting the second solvent is 2-3 wt%. Preferably, in a preferred embodiment of the present invention, the second solvent is water, and the obtained composite membrane has better mechanical properties. Preferably, the concentration of the diluted solution is 2, 2.5, 3wt%, etc., and the solution of the sulfonated aromatic polymer with such concentration can ensure that the sulfonated aromatic polymer is filled and compacted in the three-dimensional framework.
The preparation method of the sulfonated aromatic polymer comprises the following steps: mixing aromatic polymer with 98wt% sulfuric acid and 40-60 deg.C, stirring for 4-8 hr, wherein the ratio of aromatic polymer to 98wt% sulfuric acid is 0.05g/ml (for example, 25g aromatic polymer and 500ml 98wt% sulfuric acid are stirred at 50 deg.C for 4-8 hr), slowly pouring the mixed solution into a large amount of ice water, washing to neutrality, filtering, squeezing to remove water, and oven drying at 80 deg.C. In a preferred embodiment of the present invention, the sulfonated aromatic polymer has a degree of sulfonation of 65 to 85%. More preferably, the sulfonation degree of the sulfonated aromatic polymer is 70 to 80%, and the sulfonated aromatic polymer with the sulfonation degree has more excellent comprehensive performance when being applied to the invention.
Wherein the sulfonated aromatic polymer is any one of sulfonated polyaryletherketone, sulfonated polyarylethersulfone, sulfonated polyarylsulfone and sulfonated polyphenylene oxide.
Wherein, the drying is performed at 20-40 ℃, for example, at 20 ℃, 30 ℃ or 40 ℃, so that two solvents with different boiling points are slowly volatilized at the same time, and the sulfonated aromatic polymer is ensured to be tightly filled in the three-dimensional framework.
The dopamine modified three-dimensional framework is formed by self-polymerization of levodopa in a triisopropylethanesulfonyl aqueous solution on the surface of the three-dimensional framework to form a coating layer, so that the compatibility of the coating layer with a sulfonated aromatic polymer can be effectively improved. Specifically, the polydopamine modified three-dimensional framework is prepared by the following steps:
1) preparing triisopropylethanesulfonyl solution with the concentration of 0.3-0.6 mmol/L. Preferably, the concentration is 0.3, 0.4, 0.5 or 0.6mmol/L, and the triisopropylethanesulfonyl solution at the concentration is more favorable for the self-polymerization of the levodopa;
2) adding a three-dimensional framework into the aqueous solution of triisopropyl ethanesulfonyl, wherein the ratio of the three-dimensional framework to the aqueous solution of triisopropyl ethanesulfonyl is 4 g/L;
3) adding levodopa into a triisopropylethanesulfonyl aqueous solution until the concentration of the levodopa is 0.4-1 g/L, and stirring for 24 hours to obtain the polydopamine modified three-dimensional framework. Preferably, the concentration of the obtained levodopa is 0.4 to 1g/L, for example, 0.4, 0.6, 0.8 or 1g/L, within which range the coating of polydopamine is more uniform. Wherein, the porosity of three-dimensional skeleton is 85%, and thickness is 60um, and length width is 10 cm.
The three-dimensional framework is any one of electro-spun polyvinylidene fluoride nano-fiber, electro-spun polyacrylonitrile nano-fiber, porous polytetrafluoroethylene and polypropylene non-woven fabric.
In addition, the invention also provides a three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane prepared by the preparation method of the three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane.
Wherein the mass ratio of the sulfonated aromatic polymer to the polydopamine modified three-dimensional skeleton is 7: 1-7. More preferably, the mass ratio of the sulfonated aromatic polymer to the polydopamine modified three-dimensional skeleton is 7:2-4, for example, 7:2, 7:3 or 7:4, and the composite membrane within the range has better mechanical property, proton conductivity and alcohol resistance.
Preferably, the thickness of the three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane is 70-100 μm. Within this range, the proton exchange effect is better, and the thickness of the composite proton exchange membrane can be, for example, 70 μm, 80 μm, 90 μm or 100 μm, and the like, and can be set within this range by those skilled in the art according to actual needs.
Compared with the prior art, the composite proton exchange membrane and the preparation method thereof provided by the invention have the beneficial effects that: the sulfonated aromatic polymer has high proton conductivity; the three-dimensional framework effectively inhibits the swelling of the sulfonated aromatic polymer, and the mechanical property and methanol resistance of the composite membrane are improved; the modification of the polydopamine enables the combination between the three-dimensional framework and the sulfonated aromatic polymer to be tighter, and further improves the mechanical property and the methanol permeation resistance of the composite membrane.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a total reflection Raman infrared spectroscopy (ATR-FTIR) chart of an electrospun polyvinylidene fluoride nanofiber membrane (PVDF) and a polydopamine modified electrospun polyvinylidene fluoride nanofiber membrane (PDA @ PVDF) prepared by the invention.
FIG. 2 is a Scanning Electron Microscope (SEM) cross-sectional view of the proton exchange membrane of the three-dimensional framework and sulfonated aromatic polymer composite prepared by the present invention.
Fig. 3 is a stress-strain curve diagram of the sulfonated polyaryletherketone membrane (SPEEK), the sulfonated polyaryletherketone/electrospun polyvinylidene fluoride nanofiber composite proton exchange membrane (SPEEK/PVDF) and the sulfonated polyaryletherketone/polydopamine modified electrospun polyvinylidene fluoride nanofiber composite proton exchange membrane (SPEEK/PDA @ PVDF).
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The composite proton exchange membrane and the preparation method thereof according to the embodiment of the present invention are specifically described below.
A preparation method of a three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane comprises the following steps:
dissolving the sulfonated aromatic polymer in a first solvent, and then diluting with a second solvent;
placing the polydopamine modified three-dimensional framework in a film casting groove;
and pouring the sulfonated aromatic polymer solution onto the polydopamine modified three-dimensional framework, and drying to obtain the three-dimensional framework/polyelectrolyte composite proton exchange membrane.
Preferably, the drying is performed at 20-40 ℃, for example, at 20 ℃, 30 ℃ or 40 ℃, so that two solvents with different boiling points are volatilized simultaneously, and the sulfonated aromatic polymer is ensured to be filled and compact in the three-dimensional framework.
In the invention, the sulfonated aromatic polymer is prepared by stirring 25g of aromatic polymer and 500ml of 98wt% sulfuric acid at 50 ℃ for 4-8h, then slowly pouring the mixed solution into a large amount of ice water for cleaning until the mixed solution is neutral, and finally drying at 80 ℃.
The first solvent is any one or a mixture of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, and preferably, in a preferred embodiment of the invention, the first solvent is N, N-dimethylacetamide, and the conductivity of the obtained composite membrane is higher. Preferably, the concentration of the sulfonated aromatic polymer solution obtained by dissolving the first solvent is 6 to 10wt%, for example, the solution concentration is 6, 7, 8, 9, 10wt%, etc., and the solution of the sulfonated aromatic polymer having such a concentration has dilutability and film-forming property.
The second solvent is any one or a mixture of methanol, ethanol and water, preferably, in a preferred embodiment of the invention, the second solvent is water, and the obtained composite membrane has better mechanical properties. The concentration of the sulfonated aromatic polymer solution obtained by diluting with the second solvent is preferably 2 to 3wt%, for example, the concentration of the solution is 2, 2.5, 3wt%, etc., and the sulfonated aromatic polymer solution with such a concentration can ensure the sulfonated aromatic polymer to be filled densely in the three-dimensional skeleton.
The three-dimensional skeleton modified by the polydopamine is formed by the self-polymerization of the levodopa in a triisopropylethanesulfonyl aqueous solution on the surface of the three-dimensional skeleton to form a coating layer, so that the compatibility of the coating layer with a sulfonated aromatic polymer can be effectively improved. In a preferred embodiment of the invention, the polydopamine modified three-dimensional skeleton is prepared by:
firstly, preparing an aqueous solution of triisopropylethanesulfonyl chloride, preferably, the concentration of the aqueous solution of triisopropylethanesulfonyl chloride is 0.3-0.6 mmol/L, for example, the concentration of the aqueous solution of triisopropylethanesulfonyl chloride is 0.3, 0.4, 0.5 or 0.6mmol/L, and the aqueous solution of triisopropylethanesulfonyl chloride at the concentration is more beneficial to the self-polymerization of levodopa;
secondly, adding a three-dimensional framework into an aqueous solution of triisopropyl ethanesulfonyl, wherein the ratio of the three-dimensional framework to the aqueous solution of triisopropyl ethanesulfonyl is 4 g/L;
finally, levodopa is added to the aqueous solution of triisopropylethanesulfonyl chloride and stirred for 24 hours to obtain a polydopamine-modified three-dimensional skeleton, preferably with a concentration of 0.4 to 1g/L, for example, 0.4, 0.6, 0.8 or 1g/L, within which the coating of polydopamine is more uniform.
The three-dimensional framework is any one of electro-spun polyvinylidene fluoride nano-fiber, electro-spun polyacrylonitrile nano-fiber, porous polytetrafluoroethylene and polypropylene non-woven fabric.
Preferably, the mass ratio of the sulfonated aromatic polymer to the polydopamine-modified three-dimensional skeleton is 7:1-7, more preferably, the mass ratio of the sulfonated aromatic polymer to the polydopamine-modified electrospun polyvinylidene fluoride nanofiber membrane is 7:2-4, for example, the mass ratio is 7:2, 7:3 or 7:4, and the composite membrane in the range has better mechanical properties, proton conductivity and alcohol resistance.
Preferably, the thickness of the composite proton exchange membrane is 70-100 μm, and the proton exchange effect is better in the thickness range, and the thickness of the composite proton exchange membrane can be 70 μm, 80 μm, 90 μm or 100 μm, etc., and the range can be set by workers in the field according to actual needs.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
(1) Weighing 25g of sulfonated polyaryletherketone, stirring the sulfonated polyaryletherketone and 500ml of sulfuric acid for 6 hours at 50 ℃, then slowly pouring the mixed solution into a large amount of ice water, reversely washing the precipitated sulfonated polyaryletherketone with deionized water to be neutral, filtering, squeezing out water, and drying at 80 ℃ to obtain sulfonated polyaryletherketone with the sulfonation degree of 75%;
(2) dissolving 0.7g of sulfonated polyaryletherketone obtained in the step (1) in N, N-dimethylacetamide to form a 7 wt% solution; then diluting the solution with water to a 2.5 wt% solution;
(3) preparing an aqueous solution of triisopropylethanesulfonyl chloride with the concentration of 0.4 mmol/L; then adding the electrospun polyvinylidene fluoride nanofiber membrane into an aqueous solution of triisopropyl ethanesulfonyl, wherein the ratio of the polyvinylidene fluoride nanofiber membrane to the aqueous solution of triisopropyl ethanesulfonyl is 4 g/L; finally, adding levodopa into the aqueous solution of triisopropylethanesulfonyl, and stirring for 24 hours to prepare a polydopamine-modified electrospun polyvinylidene fluoride nanofiber membrane, wherein the concentration of the levodopa is 0.8 g/L;
(4) flatly paving the polydopamine modified electrospun polyvinylidene fluoride nanofiber membrane obtained in the step (3) on a glass plate, pouring the solution obtained in the step (2) on the glass plate, drying at 30 ℃, and uncovering the membrane to obtain a sulfonated polyaryletherketone/polydopamine modified electrospun polyvinylidene fluoride nanofiber composite membrane;
for comparison, the solution obtained in the step (2) of the example 1 is respectively poured on a blank glass plate and the electrospun polyvinylidene fluoride nanofiber membrane obtained in the step (3), dried at 30 ℃, and the membrane is uncovered; respectively obtaining sulfonated polyaryletherketone and sulfonated polyaryletherketone/electrospun polyvinylidene fluoride nanofiber composite membranes;
TABLE 1 Ionic conductivity, methanol permeability and mechanical Properties of sulfonated polyaryletherketone, sulfonated polyaryletherketone/electrospun polyvinylidene fluoride nanofiber composite membranes and sulfonated polyaryletherketone/polydopamine modified electrospun polyvinylidene fluoride nanofiber composite membranes
From the results in table 1, it can be seen that the ionic conductivity of the sulfonated polyaryletherketone/polydopamine modified electrospun polyvinylidene fluoride nanofiber composite membrane prepared in this example is higher than that of both the sulfonated polyaryletherketone membrane and the sulfonated polyaryletherketone/electrospun polyvinylidene fluoride nanofiber composite membrane, and the toughness of the composite membrane is also greatly improved compared with that of the sulfonated polyaryletherketone membrane and the sulfonated polyaryletherketone/electrospun polyvinylidene fluoride nanofiber composite membrane. Can meet the use requirement of the direct methanol fuel cell.
Example 2
(1) Weighing 25g of sulfonated polyaryletherketone, stirring the sulfonated polyaryletherketone and 500ml of sulfuric acid at 50 ℃ for 8 hours, slowly pouring the mixed solution into a large amount of ice water, reversely washing the precipitated sulfonated polyaryletherketone with deionized water to be neutral, filtering, squeezing out water, and drying at 80 ℃ to obtain sulfonated polyaryletherketone with the sulfonation degree of 85%;
(2) dissolving 0.7g of sulfonated aromatic polymer obtained in the step (1) in N, N-dimethylacetamide to form a 10wt% solution; then diluting the solution with water to a 3wt% solution;
(3) preparing an aqueous solution of triisopropylethanesulfonyl chloride with the concentration of 0.4 mmol/L; then adding the electrospun polyvinylidene fluoride nanofiber membrane into an aqueous solution of triisopropyl ethanesulfonyl, wherein the ratio of the polyvinylidene fluoride nanofiber membrane to the aqueous solution of triisopropyl ethanesulfonyl is 4 g/L; finally, adding levodopa into the aqueous solution of triisopropylethanesulfonyl, and stirring for 24 hours to prepare a polydopamine-modified electrospun polyvinylidene fluoride nanofiber membrane, wherein the concentration of the levodopa is 0.4 g/L;
(4) and (3) flatly paving the polydopamine modified electrospun polyvinylidene fluoride nanofiber membrane obtained in the step (3) on a glass plate, pouring the solution obtained in the step (2) on the glass plate, drying at 30 ℃, and uncovering the membrane to obtain the sulfonated polyaryletherketone/polydopamine modified electrospun polyvinylidene fluoride nanofiber composite membrane.
Example 3
(1) Weighing 25g of sulfonated polyarylether sulfone, stirring with 500ml of sulfuric acid at 50 ℃ for 4 hours, slowly pouring the mixed solution into a large amount of ice water, reversely washing the precipitated sulfonated polyarylether sulfone with deionized water to be neutral, filtering, squeezing out water, and drying at 80 ℃ to obtain sulfonated polyarylether sulfone with the sulfonation degree of 70%;
(2) dissolving 0.7g of sulfonated polyarylethersulfone obtained in the step (1) in N, N-dimethylacetamide to form a 7 wt% solution; then diluting the solution with water to a 2.5 wt% solution;
(3) preparing an aqueous solution of triisopropylethanesulfonyl chloride with the concentration of 0.4 mmol/L; then adding the electrospun polyvinylidene fluoride nanofiber membrane into an aqueous solution of triisopropyl ethanesulfonyl, wherein the ratio of the polyvinylidene fluoride nanofiber membrane to the aqueous solution of triisopropyl ethanesulfonyl is 4 g/L; finally, adding levodopa into the aqueous solution of triisopropylethanesulfonyl, and stirring for 24 hours to prepare a polydopamine-modified electrospun polyvinylidene fluoride nanofiber membrane, wherein the concentration of the levodopa is 0.8 g/L;
(4) and (3) flatly paving the polydopamine modified electrospun polyvinylidene fluoride nanofiber membrane obtained in the step (3) on a glass plate, pouring the solution obtained in the step (2) on the glass plate, drying at 30 ℃, and uncovering the membrane to obtain the sulfonated polyarylethersulfone/polydopamine modified electrospun polyvinylidene fluoride nanofiber composite membrane.
Example 4
(1) Weighing 25g of sulfonated polyphenyl ether, stirring the sulfonated polyphenyl ether and 500ml of sulfuric acid at 50 ℃ for 6 hours, slowly pouring the mixed solution into a large amount of ice water, reversely washing the precipitated sulfonated polyphenyl ether with deionized water to be neutral, filtering and squeezing water, and drying at 80 ℃ to obtain the sulfonated polyphenyl ether with the sulfonation degree of 75%;
(2) dissolving 0.7g of sulfonated aromatic polymer obtained in the step (1) in N, N-dimethylacetamide to form a 7 wt% solution; then diluting the solution with water to a 2.5 wt% solution;
(3) preparing an aqueous solution of triisopropylethanesulfonyl chloride with the concentration of 0.6 mmol/L; then adding the polypropylene non-woven fabric into an aqueous solution of triisopropyl ethanesulfonyl, wherein the ratio of the polypropylene non-woven fabric to the aqueous solution of triisopropyl ethanesulfonyl is 4 g/L; finally, adding levodopa into the aqueous solution of triisopropylethanesulfonyl, and stirring for 24 hours to prepare a polydopamine-modified electrospun polyvinylidene fluoride nanofiber membrane, wherein the concentration of the levodopa is 0.4 g/L;
(4) and (3) flatly paving the polydopamine modified polypropylene non-woven fabric obtained in the step (3) on a glass plate, pouring the solution obtained in the step (2) on the glass plate, drying at 30 ℃, and uncovering the membrane to obtain the sulfonated polyphenyl ether/polydopamine modified polypropylene non-woven fabric composite membrane.
Table 2 shows the performance index data of the sulfonated aromatic polymer/polydopamine modified three-dimensional framework composite membrane prepared in example 2-4.
TABLE 2 Ionic conductivity, methanol permeability and mechanical properties of sulfonated polyether ether ketone/polydopamine modified electrospun polyvinylidene fluoride nanofiber composite membranes, sulfonated polyether sulfone/polydopamine modified electrospun polyvinylidene fluoride nanofiber composite membranes and sulfonated polyphenylene oxide/polydopamine modified polypropylene non-woven fabric composite membranes
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 1-106Hz, and the amplitude of the alternating current signal is 50 mV. The cut films (length × width ═ 2.5cm × 1.5cm) were tested using the two-electrode ac impedance method, and prior to testing, the film samples were saturated in room temperature deionized water. Ionic conductance of membranesThe ratio σ (S/cm) is 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 through an alternating current impedance test is obtained.
(2) Methanol permeability: the methanol permeation caused by the methanol concentration gradient was measured by diffusion. The membrane was sandwiched between two identical compartments, wherein equal amounts of methanol solution and water were added to the two compartments, respectively, with stirring at ambient temperature. The change in methanol concentration was determined by gas chromatography. Methanol permeability is calculated from the following equation:
wherein P is methanol permeability (cm)2In s). l and A are the thickness (cm) and area (cm) of the permeability, respectively2). V and CoVolume (cm) of methanol solution respectively3) And initial concentration (mol/L). Δ C/Δ t is the slope of the methanol concentration in the water compartment over time.
(3) Tensile strength and 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.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be regarded as equivalents and are intended to be included within the scope of the invention.
Claims (7)
1. A preparation method of a three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane is characterized by comprising the following steps:
1) dissolving the sulfonated aromatic polymer in a first solvent, and then diluting with a second solvent;
2) pouring the sulfonated aromatic polymer solution obtained in the step 1) on a polydopamine modified three-dimensional framework, drying to obtain the composite proton exchange membrane,
the first solvent is any one or a mixture of several of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, and the concentration of the sulfonated aromatic polymer solution obtained by dissolving the first solvent is 6-10 wt%; the second solvent is any one or a mixture of methanol, ethanol and water, and the concentration of the sulfonated aromatic polymer solution obtained by diluting the second solvent is 2-3 wt%;
wherein the polydopamine modified three-dimensional skeleton is prepared by the following steps:
1) preparing triisopropyl ethanesulfonyl aqueous solution with the concentration of 0.3-0.6 mmol/L;
2) adding a three-dimensional framework into the aqueous solution of triisopropyl ethanesulfonyl, wherein the ratio of the three-dimensional framework to the aqueous solution of triisopropyl ethanesulfonyl is 4 g/L;
3) adding levodopa into a triisopropylethanesulfonyl aqueous solution until the concentration of the levodopa is 0.4-1 g/L, and stirring for 24 hours to obtain the polydopamine modified three-dimensional framework.
2. The method for preparing the proton exchange membrane compounded by the three-dimensional framework and the sulfonated aromatic polymer as claimed in claim 1, wherein the method comprises the following steps: the preparation method of the sulfonated aromatic polymer comprises the following steps: mixing aromatic polymer with 98wt% sulfuric acid at 40-60 deg.C, stirring for 4-8h, wherein the dosage ratio of aromatic polymer to 98wt% sulfuric acid is 0.05g/ml, slowly pouring the mixed solution into a large amount of ice water, cleaning to neutrality, filtering, squeezing to remove water, and oven drying at 80 deg.C.
3. The method for preparing the proton exchange membrane compounded by the three-dimensional framework and the sulfonated aromatic polymer as claimed in claim 1, wherein the method comprises the following steps: the sulfonated aromatic polymer is any one of sulfonated polyaryletherketone, sulfonated polyarylethersulfone, sulfonated polyarylsulfone and sulfonated polyphenylene oxide.
4. The method for preparing the proton exchange membrane compounded by the three-dimensional framework and the sulfonated aromatic polymer as claimed in claim 1, wherein the method comprises the following steps: the three-dimensional framework is any one of electro-spun polyvinylidene fluoride nano-fiber, electro-spun polyacrylonitrile nano-fiber, porous polytetrafluoroethylene and polypropylene non-woven fabric.
5. The proton exchange membrane compounded by the three-dimensional framework and the sulfonated aromatic polymer is characterized by being prepared by the preparation method of the proton exchange membrane compounded by the three-dimensional framework and the sulfonated aromatic polymer according to any one of claims 1 to 4.
6. The proton exchange membrane of claim 5 wherein the mass ratio of the sulfonated aromatic polymer to the polydopamine modified three-dimensional skeleton is 7: 1-7.
7. The three-dimensional framework and sulfonated aromatic polymer composite proton exchange membrane according to claim 5, wherein the thickness is 70-100 μm.
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| CN111048812A (en) * | 2019-12-26 | 2020-04-21 | 先进储能材料国家工程研究中心有限责任公司 | Proton exchange composite membrane and preparation method thereof |
| CN112687927B (en) * | 2020-12-25 | 2022-06-21 | 南京大学 | High-durability fuel cell composite proton exchange membrane and preparation method and application thereof |
| CN113346116B (en) * | 2021-05-20 | 2022-11-01 | 华中科技大学 | Polydopamine-modified hollow metal organic framework-modified polymer hybrid proton exchange membrane and preparation thereof |
| CN113314748B (en) * | 2021-05-31 | 2022-09-02 | 安徽中能元隽氢能科技股份有限公司 | Preparation method of enhanced proton exchange membrane based on surface modified polymer framework |
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