CN111303630A - Ultraviolet light induced gradient distribution POSS microsphere/polyarylether sulfone based composite proton exchange membrane and preparation method thereof - Google Patents

Ultraviolet light induced gradient distribution POSS microsphere/polyarylether sulfone based composite proton exchange membrane and preparation method thereof Download PDF

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CN111303630A
CN111303630A CN202010154583.9A CN202010154583A CN111303630A CN 111303630 A CN111303630 A CN 111303630A CN 202010154583 A CN202010154583 A CN 202010154583A CN 111303630 A CN111303630 A CN 111303630A
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sulfonated
octa
membrane
maposs
polyarylether sulfone
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CN111303630B (en
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陈芳
董文洁
林锋
马晓燕
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Jiangsu Aihe Composite Materials Co ltd
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Northwestern Polytechnical University
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Abstract

The invention relates to an ultraviolet light induced gradient distribution POSS microsphere/polyarylether sulphone based composite proton exchange membrane and a preparation method thereof, wherein pure polysulfone with high sulphonation degree is adopted as a matrix, an otca-MAPOS (octamethacryloxypropyl POSS)/sulfonated polyarylether sulphone composite coating is coated on the surface of the pure polysulfone, and the particle size of POSS nano microspheres in the coating is in gradient distribution along with the thickness, so that the composite proton exchange membrane with a sandwich structure with good interface compatibility is prepared, and the swelling rate of the sulfonated polyarylether matrix with high sulphonation degree under the conditions of high temperature and high humidity is favorably reduced. The preparation method is simple, the time period is short, the existing commercial membrane can be subjected to post-treatment modification, and large-scale commercial production is facilitated.

Description

Ultraviolet light induced gradient distribution POSS microsphere/polyarylether sulfone based composite proton exchange membrane and preparation method thereof
Technical Field
The invention belongs to the field of proton exchange membranes, and relates to an ultraviolet light induced gradient distribution POSS microsphere/polyarylethersulfone-based composite proton exchange membrane and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are generally composed of bipolar plates, gas diffusion layers, catalyst layers, and a Proton Exchange Membrane (PEM). The anode of the fuel cell is typically selectively fed with humidified H2As fuel, H obtained by oxidation of lost electrons under the action of catalyst+The electrons transported to the cathode through PEM and oxygen and external circuit generate O2To produce water. The proton conductivity of the PEM is related to the performance of the entire cell, since protons are transported from the cathode to the anode through hydrophilic groups in the PEM, which is proportional to the power density and energy of the cell. Another function of the PEM is to prevent shorting between the anode and cathode contacts. The PEM is one of the core components of the PEMFC and requires high chemical and thermal stability, good mechanical properties, high proton conductivity, low fuel permeability, etc. to meet the application requirements.
Currently used PEM materials are mainly of the following two types: one is perfluoro sulfonic acid PEM represented by Nafion, and the structure of polytetrafluoroethylene endows the PEM with high low-temperature proton conductivity (<80 ℃) and chemical stability, but perfluorosulfonic acid membranes are expensive and have high fuel leakage rates, and proton conductivity is reduced due to water evaporation at high temperatures. The other is the higher glass transition temperature (T) which is researched by researchers in recent years for solving the problem of the perfluorosulfonic acid membraneg) And chemically stable hydrocarbon-based polymers such as: polysulfones (PSF), Polybenzimidazoles (PBI), poly (I)Aromatic backbones such as imide (PI) or Polyetheretherketone (PEEK). The side chain or the side group of the ionic group is introduced into the main chain to realize the high-efficiency conduction of different types of ions by protons, when the concentration of the hydrophilic ionic group in the ionomer chain reaches a certain degree, the size of the hydrophilic ionic phase is continuously increased, the continuity of hydrophobic and nonionic phases is influenced, the swelling rate of the membrane is suddenly increased, and the mechanical property and the proton conductivity have the Trade-off effect. Therefore, in order to balance the relationship between mechanical properties and proton conductivity, the preparation of hybrid membranes by compounding nano fillers with different dimensions, chemical structures and surface properties with ionomers is a promising strategy for researchers.
Although the hybrid membrane prepared by compounding the nano-filler and the ionomer can effectively balance the relationship between the mechanical property and the proton conductivity, the premise is that the nano-filler needs to be stably and uniformly dispersed in the ionomer. The current hybrid membrane with homogeneous structure has a plurality of problems, such as: the interface is difficult to regulate and control, is unstable, is easy to agglomerate, is not uniformly dispersed and the like. The invention utilizes ultraviolet light as an induced phase-splitting self-assembly technology, and adjusts the contents of SPSF and otca-MAPOSS, the content of a photoinitiator, the illumination time (and other conditions), thereby not only realizing the stable and uniform dispersion of POSS in an ionomer, but also realizing the gradient change of the particle size of nano-scale POSS spherical particles along with the thickness of a composite film, and preparing the heterogeneous PEM material with the gradient and quantitative control of the nano-scale POSS structure. The structural gradient can realize the cooperative improvement of the strength of the gradient nano twin crystal structure material and the work hardening, and when the structural gradient is large enough, the strength of the gradient material even exceeds the strongest part in the gradient microstructure, so that the mechanical property of the nano POSS structure gradient quantitatively controllable heterogeneous PEM material is improved compared with that of a homogeneous material. The invention is hopeful to be used as a hybrid membrane material method for in-situ generating gradient nano POSS particles by ultraviolet light in-situ inducing POSS polymerization containing active groups.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides an ultraviolet light induced gradient distribution POSS microsphere/polyarylethersulfone-based composite proton exchange membrane and a preparation method thereof, and solves the problems of PEM proton conductivity reduction and swelling rate increase caused by different reaction characteristics of a cathode and an anode of the proton exchange membrane.
Technical scheme
An ultraviolet light induced gradient distribution nano Octa-MAPOSS microsphere/sulfonated polyarylether sulfone membrane is characterized by comprising a membrane matrix sulfonated polyarylether sulfone, a photoinitiator 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide TPO and a reactive POSS modifier Octa-methacryloxypropyl polysilsesquioxane Octa-MAPOS; wherein: the TPO photoinitiator accounts for 2-10% of the mass of the sulfonated polyarylether sulphone, and the octa-MAPOSS accounts for 5-15% of the mass of the sulfonated polyarylether sulphone.
The sulfonated polyarylether sulfone takes DMF (dimethyl formamide) as a solvent to prepare 0.1-0.5 g/mL of sulfonated polyarylether sulfone solution, and the sulfonation degree of the sulfonated polyarylether sulfone ranges from 20% to 50%.
A method for preparing the ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylethersulfone membrane is characterized by comprising the following steps:
step 1, preparing a casting solution: preparing 0.1-0.5 g/mL sulfonated polyarylether sulfone solution by using DMF (dimethyl formamide) as a solvent, and mixing the sulfonated polyarylether sulfone solution with a photoinitiator 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) and a reactive POSS (polyhedral oligomeric silsesquioxane) modifier octamethacryloxypropyl polysilsesquioxane Octa-MAPOS; the TPO photoinitiator accounts for 2-10% of the mass of the sulfonated polyarylether sulfone, and the octa-MAPOSS accounts for 5-15% of the mass of the sulfonated polyarylether sulfone; the range of the sulfonation degree of the sulfonated polyarylethersulfone is 20-50%;
step 2: and then uniformly mixing the materials at 25 ℃ and 50% RH, preparing a membrane by adopting a blade coating method, irradiating a liquid membrane for 1-30 min under an ultraviolet lamp of 30-300W, and finally placing the membrane in a vacuum drying oven at 40 ℃ until the solvent is completely volatilized to obtain the ultraviolet-induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone membrane.
When the thickness of the liquid film is between 100 +/-5 and 200 +/-5 mu m, the thickness of the dried film is between 20 +/-5 and 30 +/-5 mu m.
The wavelength of the ultraviolet lamp is 365 nm.
The commercial sulfonated polysulfone is soaked in 0.05g/mL sulfuric acid and washed to be neutral by deionized water, and can be used after being dried.
A method for preparing a sandwich-structure composite proton exchange membrane containing gradient distribution nano octa-MAPOSS microspheres/sulfonated polyarylether sulfone coating by utilizing an ultraviolet light induced gradient distribution nano octa-MAPOSS microspheres/sulfonated polyarylether sulfone membrane is characterized in that:
step (1): coating a layer of pure polyarylether sulfone solution with the concentration of 0.4g/mL on an ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone film as a substrate, and placing the substrate in a vacuum drying oven at the temperature of 40 ℃ until the solvent is completely volatilized; the sulfonation degree of the pure polyarylethersulfone solution is 60-70%;
step (2): preparing an ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone film on the basis of the dried film to obtain a gradient distribution nano octa-MAPOSS microsphere/medium sulfonated polyarylether sulfone coating/high sulfonation degree polyarylether sulfone matrix/gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone coating;
the thickness ratio range of the three-layer membrane of the sandwich-structure PEM is controlled to be 1:2: 1-1: 4: 1.
The total film thickness is controlled to be 40-60 mu m.
The thickness of the liquid film after the step (1) is finished is (90+10) + -5 to (240+10) + -5 mu m, and the thickness of the dried layer film is (20+10) + -5 to (40+10) + -5 mu m.
After the step (2) is finished, the thickness of the liquid film is (60+30) + -5 to (60+50) + -5 mu m, and the thickness of the dried layer film is (10+30) + -5 to (10+50) + -5 mu m.
Advantageous effects
The invention provides an ultraviolet light induced gradient distribution POSS microsphere/polyarylether sulfone based composite proton exchange membrane and a preparation method thereof.
The invention provides a method for preparing a gradient-distributed composite proton exchange membrane by ultraviolet light induction, wherein POSS balls in gradient distribution are uniformly distributed in sulfonated polyarylethersulfone, the particle sizes of the POSS balls from a light irradiation surface to a lower part are in gradient distribution, the unique structural distribution is caused by energy decrement in the ultraviolet light irradiation process, the uniform and gradient-distributed POSS balls can reduce the swelling of the membrane to a certain extent, the mechanical stability of the membrane is ensured, the methanol permeation can be reduced, but the proton conductivity can be reduced by adding the POSS, so the POSS is compounded with a substrate with high sulfonation degree, and a certain proton conductivity is ensured.
Compared with the prior materials and technologies, the invention has the following advantages:
1) the POSS/sulfonated polyarylethersulfone membrane with gradient distribution prepared by ultraviolet light induction can reduce the swelling of the membrane and ensure the mechanical stability of the membrane;
2) the proton conductivity of the composite PEM with the sandwich structure in the full hydration test state is not greatly reduced;
3) the preparation method is simple, the time period is short, the existing commercial membrane can be subjected to post-treatment modification, and large-scale commercial production is facilitated.
Drawings
FIG. 1: ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone membrane
FIG. 2: preparation flow chart of composite proton exchange membrane with sandwich structure
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
preparing an ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone membrane:
step 1, preparing a casting solution: DMF is used as a solvent to prepare 0.1-0.5 g/mL sulfonated polyarylethersulfone solution, wherein the mass fraction of TPO photoinitiator is 2-10%, and the mass fraction of octa-MAPOSS is 5-15%.
Step 2, film preparation: : the components are uniformly mixed at 25 ℃ and 50% RH, a blade coating method is adopted for preparing the membrane, the scraped membrane is irradiated for 1-30 min under an ultraviolet lamp of 30-300W, and finally the membrane is placed in a vacuum drying oven at 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be 100 +/-5, 150 +/-5 and 200 +/-5 mu m, and the thickness of the finally dried film is controlled to be 20 +/-5, 25 +/-5 and 30 +/-5 mu m.
When the conditions for preparing the ultraviolet light induced gradient distribution nano octa-MAPOS microspheres/sulfonated polyarylether sulfone coating with optimal performance are found, the sandwich structure composite proton exchange membrane of the gradient distribution nano octa-MAPOS microspheres/sulfonated polyarylether sulfone coating is prepared according to the following process:
the structure of the composite proton exchange membrane with the sandwich structure is as follows: the gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone coating/high sulfonation degree sulfonated polyarylether sulfone matrix/gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone coating comprises the following specific preparation steps:
step 1: preparing a gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylethersulfone coating: preparing 0.4g/mL sulfonated polyarylethersulfone solution by using DMF as a solvent, respectively adding 10% of TPO and 15% of octa-MAPOSS into the prepared sulfonated polyarylethersulfone solution, uniformly mixing the components at 25 ℃ and 50% of RH, preparing a membrane by adopting a blade coating method, illuminating the scraped membrane for 30min under a 32W ultraviolet lamp, and finally placing the membrane in a vacuum drying oven at 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be 60 +/-5 mu m, and the thickness of the dried film is 10 +/-5 mu m.
The sulfonation degree of the sulfonated polyarylethersulfone is 40-50%.
Step 2: preparing a sulfonated polyarylethersulfone matrix membrane: and (3) coating a layer of pure sulfonated polyarylethersulfone solution with the concentration of 0.4g/mL on the dried composite membrane as a substrate by scraping, and finally placing the composite membrane in a vacuum drying oven at the temperature of 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be (90+10) ± 5, (140+10) ± 5, (190+10) ± 5, (240+10) ± 5 μm, and the thickness of the dried film is (20+10) ± 5, (25+10) ± 5, (30+10) ± 5, (40+10) ± 5 μm.
The sulfonation degree of the sulfonated polyarylethersulfone is 60-70%.
And step 3: preparing a composite proton exchange membrane with a sandwich structure: repeating the step 1 on the basis of the dried film in the step 2, controlling the thickness of the liquid film to be (60+30) ± 5, (60+35) ± 5, (60+40) ± 5, (60+50) ± 5 μm, and controlling the thickness of the dried film to be (10+30) ± 5, (10+35) ± 5, (10+40) ± 5, (10+50) ± 5 μm.
The invention is mainly designed from the following aspects: the invention discloses a method for realizing uniform particle size distribution of POSS spheres and controlling the particle size distribution in a nanometer size range by changing the content of a photoinitiator, the concentration of a polymer solution, the content of POSS, the illumination intensity and the illumination time, and the method is simple and easy to operate and has wide practicability on chemical compositions of proton exchange membrane matrixes (sulfonated polysulfone, sulfonated polyether ether ketone and the like). The same material is adopted for compounding, so that the compatibility between the composite membranes is better, and the cycle life of the fuel cell is prolonged. And secondly, preparing the composite PEM with a sandwich structure by regulating the thicknesses of the composite layer and the substrate layer. The prepared heterostructure composite PEM not only has good interface compatibility, but also reduces the swelling rate of the membrane while the proton conductivity is not greatly reduced.
The above object of the present invention is solved by the following technical solutions:
step 1: preparing a gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylethersulfone coating: preparing 0.4g/mL sulfonated polyarylethersulfone solution by using DMF as a solvent, respectively adding 10% of TPO and 15% of octa-MAPOSS into the prepared sulfonated polyarylethersulfone solution, uniformly mixing the components at 25 ℃ and 50% of RH, preparing a membrane by adopting a blade coating method, illuminating the scraped membrane for 30min under a 32W ultraviolet lamp, and finally placing the membrane in a vacuum drying oven at 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be 60 +/-5 mu m, and the thickness of the dried film is 10 +/-5 mu m.
The sulfonation degree of the sulfonated polyarylethersulfone is 40-50%.
Step 2: preparing a sulfonated polyarylethersulfone matrix membrane: and (3) coating a layer of pure sulfonated polyarylethersulfone solution with the concentration of 0.4g/mL on the dried composite membrane as a substrate by scraping, and finally placing the composite membrane in a vacuum drying oven at the temperature of 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be (90+10) ± 5, (140+10) ± 5, (190+10) ± 5, (240+10) ± 5 μm, and the thickness of the dried film is (20+10) ± 5, (25+10) ± 5, (30+10) ± 5, (40+10) ± 5 μm.
The sulfonation degree of the sulfonated polyarylethersulfone is 60-70%.
And step 3: preparing a composite proton exchange membrane with a sandwich structure: repeating the step 1 on the basis of the dried film in the step 2, controlling the thickness of the liquid film to be (60+30) ± 5, (60+35) ± 5, (60+40) ± 5, (60+50) ± 5 μm, and controlling the thickness of the dried film to be (10+30) ± 5, (10+35) ± 5, (10+40) ± 5, (10+50) ± 5 μm.
Example 1
Preparing an ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone membrane:
preparing 0.4g/mL sulfonated polyarylethersulfone solution by using DMF as a solvent, respectively adding 2.5 mass percent of TPO and 15 mass percent of octa-MAPOSS into the prepared sulfonated polyarylethersulfone solution, uniformly mixing the components at 25 ℃ and 50% RH, preparing a membrane by adopting a blade coating method, illuminating the scraped membrane for 30min under a 32W ultraviolet lamp, and finally placing the membrane in a vacuum drying oven at 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be 200 + -5 μm, and the thickness of the dried film is controlled to be 30+ -5 μm.
Example 2
Preparing an ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone membrane:
preparing 0.4g/mL sulfonated polyarylethersulfone solution by using DMF as a solvent, respectively adding 5% of TPO and 15% of octa-MAPOSS into the prepared sulfonated polyarylethersulfone solution, uniformly mixing the components at 25 ℃ and 50% of RH, preparing a membrane by adopting a blade coating method, illuminating the scraped membrane for 30min under a 32W ultraviolet lamp, and finally placing the membrane in a vacuum drying oven at 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be 200 + -5 μm, and the thickness of the dried film is controlled to be 30+ -5 μm.
Example 3
Preparing an ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone membrane:
preparing 0.4g/mL sulfonated polyarylethersulfone solution by using DMF as a solvent, respectively adding 2.5 mass percent of TPO and 15 mass percent of octa-MAPOSS into the prepared sulfonated polyarylethersulfone solution, uniformly mixing the components at 25 ℃ and 50% RH, preparing a membrane by adopting a blade coating method, illuminating the scraped membrane for 30min under a 32W ultraviolet lamp, and finally placing the membrane in a vacuum drying oven at 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be 150 + -5 μm, and the thickness of the dried film is controlled to be 25+ -5 μm.
The measured performance data for the films prepared in the above examples are shown in the following table:
Figure BDA0002403626960000081
example 4
A method for preparing a sandwich-structure composite proton exchange membrane containing gradient distribution nano octa-MAPOSS microspheres/sulfonated polyarylethersulfone coating comprises the following processes:
(1) preparing a gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylethersulfone coating: preparing 0.4g/mL sulfonated polyarylethersulfone solution by using DMF as a solvent, respectively adding 10% of TPO and 15% of octa-MAPOSS into the prepared sulfonated polyarylethersulfone solution, uniformly mixing the components at 25 ℃ and 50% of RH, preparing a membrane by adopting a blade coating method, illuminating the scraped membrane for 30min under a 32W ultraviolet lamp, and finally placing the membrane in a vacuum drying oven at 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be 60 +/-5 mu m, and the thickness of the dried film is 10 +/-5 mu m.
The sulfonation degree of the sulfonated polyarylethersulfone is 50%.
(2) Preparing a sulfonated polyarylethersulfone matrix membrane: and (3) coating a layer of pure sulfonated polyarylethersulfone solution with the concentration of 0.4g/mL on the dried composite membrane as a substrate by scraping, and finally placing the composite membrane in a vacuum drying oven at the temperature of 40 ℃ until the solvent is completely volatilized. The thickness of the liquid film is controlled to be (140+ 10). + -. 5 μm, and the thickness of the dried film is controlled to be (25+ 10). + -. 5 μm.
The sulfonation degree of the sulfonated polyarylethersulfone is 60%.
(3) Preparing a composite proton exchange membrane with a sandwich structure: repeating the step 1 on the basis of the dried film in the step 2, controlling the thickness of the liquid film to be (60+30) +/-5 mu m, and controlling the thickness of the dried film to be (10+25) +/-5 mu m.
The measured performance data for the films prepared in the above examples are shown in the following table:
Figure BDA0002403626960000091
note: the composite sulfonated polysulfone substrate means that the thickness of each layer is the same as that of the composite membrane.

Claims (10)

1. An ultraviolet light induced gradient distribution nano Octa-MAPOSS microsphere/sulfonated polyarylether sulfone membrane is characterized by comprising a membrane matrix sulfonated polyarylether sulfone, a photoinitiator 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide TPO and a reactive POSS modifier Octa-methacryloxypropyl polysilsesquioxane Octa-MAPOS; wherein: the TPO photoinitiator accounts for 2-10% of the mass of the sulfonated polyarylether sulphone, and the octa-MAPOSS accounts for 5-15% of the mass of the sulfonated polyarylether sulphone.
2. The UV-induced gradient-distribution nano octa-MAPOSS microsphere/sulfonated polyarylethersulfone membrane of claim 1, wherein: the sulfonated polyarylether sulfone takes DMF (dimethyl formamide) as a solvent to prepare 0.1-0.5 g/mL of sulfonated polyarylether sulfone solution, and the sulfonation degree of the sulfonated polyarylether sulfone ranges from 20% to 50%.
3. A method for preparing the ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylethersulfone membrane of claim 1 or 2, which comprises the following steps:
step 1, preparing a casting solution: preparing 0.1-0.5 g/mL sulfonated polyarylether sulfone solution by using DMF (dimethyl formamide) as a solvent, and mixing the sulfonated polyarylether sulfone solution with a photoinitiator 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) and a reactive POSS (polyhedral oligomeric silsesquioxane) modifier octamethacryloxypropyl polysilsesquioxane Octa-MAPOS; the TPO photoinitiator accounts for 2-10% of the mass of the sulfonated polyarylether sulfone, and the octa-MAPOSS accounts for 5-15% of the mass of the sulfonated polyarylether sulfone; the range of the sulfonation degree of the sulfonated polyarylethersulfone is 20-50%;
step 2: and then uniformly mixing the materials at 25 ℃ and 50% RH, preparing a membrane by adopting a blade coating method, irradiating a liquid membrane for 1-30 min under an ultraviolet lamp of 30-300W, and finally placing the membrane in a vacuum drying oven at 40 ℃ until the solvent is completely volatilized to obtain the ultraviolet-induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone membrane.
4. The method of claim 3, wherein: when the thickness of the liquid film is between 100 +/-5 and 200 +/-5 mu m, the thickness of the dried film is between 20 +/-5 and 30 +/-5 mu m.
5. The method of claim 3, wherein: the wavelength of the ultraviolet lamp is 365 nm.
6. The method of claim 3, wherein: the commercial sulfonated polysulfone is soaked in 0.05g/mL sulfuric acid and washed to be neutral by deionized water, and can be used after being dried.
7. A method for preparing a sandwich-structure composite proton exchange membrane containing gradient distribution nano octa-MAPOSS microspheres/sulfonated polyarylether sulfone coatings by utilizing the ultraviolet light induced gradient distribution nano octa-MAPOSS microspheres/sulfonated polyarylether sulfone membranes prepared by any one of claims 3-6 is characterized by comprising the following steps of:
step (1): coating a layer of pure polyarylether sulfone solution with the concentration of 0.4g/mL on an ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone film as a substrate, and placing the substrate in a vacuum drying oven at the temperature of 40 ℃ until the solvent is completely volatilized; the sulfonation degree of the pure polyarylethersulfone solution is 60-70%;
step (2): preparing an ultraviolet light induced gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone film on the basis of the dried film to obtain a gradient distribution nano octa-MAPOSS microsphere/medium sulfonated polyarylether sulfone coating/high sulfonation degree polyarylether sulfone matrix/gradient distribution nano octa-MAPOSS microsphere/sulfonated polyarylether sulfone coating;
the thickness ratio range of the three-layer membrane of the sandwich-structure PEM is controlled to be 1:2: 1-1: 4: 1.
8. The method of claim 7, wherein: the total film thickness is controlled to be 40-60 mu m.
9. The method of claim 7, wherein: the thickness of the liquid film after the step (1) is finished is (90+10) + -5 to (240+10) + -5 mu m, and the thickness of the dried layer film is (20+10) + -5 to (40+10) + -5 mu m.
10. The method of claim 7, wherein: after the step (2) is finished, the thickness of the liquid film is (60+30) + -5 to (60+50) + -5 mu m, and the thickness of the dried layer film is (10+30) + -5 to (10+50) + -5 mu m.
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