阅读说明：本技术 一种复合型质子交换膜的制备方法 (Preparation method of composite proton exchange membrane ) 是由 郑法 董辉 刘清 谢春元 张佳颖 于 2019-10-31 设计创作，主要内容包括：本发明公开了一种复合型质子交换膜的制备方法,具体步骤如下：取HAuCl<Sub>4</Sub>与二氯化钯加入至二次蒸馏水中,加入聚乙烯吡咯烷酮,在室温下搅拌,缓慢加入至NaNH<Sub>4</Sub>溶液中,室温下搅拌,加入二次蒸馏苯胺的硫酸水溶液,室温下搅拌,再缓慢加入过硫酸铵溶液,继续搅拌,之后置于0℃下,将获得的沉淀物用二次蒸馏水和甲醇过滤,真空干燥,得到复合材料,将磺化聚醚醚酮加入二甲基甲酰胺中,再加入复合材料,搅拌分散均匀后在洁净的玻璃板上流延成膜,真空干燥,揭膜后在硫酸溶液中浸泡,用去离子水充分浸泡、洗涤,真空干燥,得复合型质子交换膜。本发明的优点在于复合型质子交换膜的机械稳定性和耐溶剂性得到提高,可广泛应用于燃料电池质子交换膜领域。(The invention discloses a preparation method of a composite proton exchange membrane, which comprises the following specific steps: taking HAuCl 4 Adding palladium dichloride into redistilled water, adding polyvinylpyrrolidone, stirring at room temperature, and slowly adding into NaNH 4 Stirring the solution at room temperature, adding a sulfuric acid aqueous solution of redistilled aniline, stirring the solution at room temperature, slowly adding an ammonium persulfate solution, continuously stirring the solution, then placing the solution at 0 ℃, filtering the obtained precipitate with redistilled water and methanol, drying the precipitate in vacuum to obtain a composite material, adding sulfonated polyether ether ketone into dimethylformamide, adding the composite material, uniformly stirring and dispersing the composite material, then casting the composite material on a clean glass plate to form a film, drying the film in vacuum, taking off the film, soaking the film in the sulfuric acid solution, fully soaking the film in deionized water, washing the film, and drying the film in vacuum to obtain the composite proton exchange membrane.The invention has the advantages that the mechanical stability and the solvent resistance of the composite proton exchange membrane are improved, and the composite proton exchange membrane can be widely applied to the field of fuel cell proton exchange membranes.)

1. The preparation method of the composite proton exchange membrane is characterized by comprising the following specific steps:

preparing a gold-palladium doped polyaniline nano composite material: taking HAuCl₄Adding palladium chloride and the mixture into the secondary distilled water, adding polyvinylpyrrolidone, stirring at room temperature for 20-40min, and slowly adding the mixture into NaNH₄Stirring the solution at room temperature for 1-3h, adding a sulfuric acid aqueous solution of redistilled aniline after the solution turns into reddish brown, then continuing to stir at room temperature for 2-3h, then slowly adding an ammonium persulfate solution, continuing to stir for 6-8h, then placing at 0 ℃ for 8-12h, filtering the obtained precipitate with redistilled water and methanol, and then drying in a vacuum drying oven at 60 ℃ for 8-12h to obtain the gold-palladium doped polyaniline nanocomposite;

preparing a composite proton exchange membrane: adding sulfonated polyether ether ketone into dimethylformamide to prepare a solution with the concentration of 5-10 wt%, then adding the gold-palladium doped polyaniline nanocomposite prepared in the step (1), stirring and dispersing uniformly, then casting the solution on a clean glass plate to form a film, drying the film in vacuum at 60 ℃ for 12-24h, removing the film, soaking the film in 1mol/L sulfuric acid solution for 1-2 h, fully soaking the film in deionized water, washing, and drying in vacuum to obtain the composite proton exchange membrane.

2. The method for preparing a composite proton exchange membrane according to claim 1, wherein the method comprises the following steps: HAuCl in the step (1)₄The molar mass ratio of the palladium chloride to the palladium dichloride is (1-1.1): 1.

3. the method for preparing a composite proton exchange membrane according to claim 1, wherein the method comprises the following steps: the addition amount of the polyvinylpyrrolidone in the step (1) is HAuCl₄And the total mass of the catalyst and palladium dichloride is more than 6 times.

4. The method for preparing a composite proton exchange membrane according to claim 1, wherein the method comprises the following steps: NaNH in the step (1)₄The concentration of the solution was 0.1 g/ml.

5. The method for preparing a composite proton exchange membrane according to claim 1, wherein the method comprises the following steps: the preparation method of the sulfuric acid aqueous solution of the twice-distilled aniline in the step (1) comprises the following steps: 0.1mol/L redistilled aniline was dissolved in 0.1mol/L sulfuric acid aqueous solution of the same volume, and stirred at room temperature for 10 min.

6. The method for preparing a composite proton exchange membrane according to claim 1, wherein the method comprises the following steps: in the step (1), the ammonium persulfate solution is 0.1mol/L, and the ammonium persulfate and HAuCl are₄Adding the mixture according to the molar weight ratio of (3-3.5): 1.

7. the method for preparing a composite proton exchange membrane according to claim 1, wherein the method comprises the following steps: the mass ratio of the sulfonated polyether ether ketone to the gold-palladium doped polyaniline nanocomposite material in the step (2) is (3.2-5): 1.

Technical Field

The invention relates to the field of proton exchange membranes, in particular to a preparation method of a composite proton exchange membrane.

Background

Proton exchange membrane fuel cells have outstanding performance and outstanding advantages, such as large working current, high specific power and specific energy density, high energy conversion efficiency, environmental friendliness, simple and convenient construction, flexibility, portability, wide fuel sources and the like. The proton exchange membrane is one of the core components of the proton exchange membrane fuel cell and plays an important role in the performance of the proton exchange membrane fuel cell. The commercialized proton exchange membrane is mainly a perfluorosulfonic acid-polytetrafluoroethylene copolymer membrane produced by DuPont, and has the defects of strong dependence of proton conductivity on water, high methanol permeability coefficient, complex synthesis process, high price and the like, so that the further development and application of the perfluorosulfonic acid-polytetrafluoroethylene copolymer membrane in the field of fuel cells are hindered. In recent years, a sulfonated aromatic polymer having a high temperature resistance and not containing fluorine has been widely studied, which has excellent thermal stability and mechanical stability and a freely designable structure, but the development thereof is restricted by the balance between proton conductivity and mechanical stability. Inorganic materials are doped in a polymer matrix, and the advantages of the inorganic materials are combined with the characteristics of a high molecular matrix to prepare the inorganic-organic composite proton exchange membrane, which is one of important methods for modifying the proton exchange membrane.

Disclosure of Invention

The invention aims to provide a preparation method of a composite proton exchange membrane.

The technical purpose of the invention is realized by the following technical scheme:

the preparation method of the composite proton exchange membrane is characterized by comprising the following specific steps:

(1) preparing a gold-palladium doped polyaniline nano composite material: taking HAuCl₄Adding palladium chloride and the mixture into the secondary distilled water, adding polyvinylpyrrolidone, stirring at room temperature for 20-40min, and slowly adding the mixture into NaNH₄Stirring at room temperature for 1-3 hr, adding sulfuric acid water solution of redistilled aniline after the solution turns into red brown, stirring at room temperature for 2-3 hr, slowly adding ammonium persulfate solution, stirring for 6-8 hr, and standing at 0 deg.CFiltering the obtained precipitate with secondary distilled water and methanol for 8-12h, and drying in a vacuum drying oven at 60 deg.C for 8-12h to obtain gold-palladium doped polyaniline nanocomposite;

(2) preparing a composite proton exchange membrane: adding sulfonated polyether ether ketone into dimethylformamide to prepare a solution with the concentration of 5-10 wt%, then adding the gold-palladium doped polyaniline nanocomposite prepared in the step (1), stirring and dispersing uniformly, then casting the solution on a clean glass plate to form a film, drying the film in vacuum at 60 ℃ for 12-24h, removing the film, soaking the film in 1mol/L sulfuric acid solution for 1-2 h, fully soaking the film in deionized water, washing, and drying in vacuum to obtain the composite proton exchange membrane.

Preferably, HAuCl is used in the step (1)₄The molar mass ratio of the palladium chloride to the palladium dichloride is (1-1.1): 1.

preferably, the polyvinylpyrrolidone in the step (1) is added in an amount of HAuCl₄And the total mass of the catalyst and palladium dichloride is more than 6 times.

Preferably, the NaNH in the step (1)₄The concentration of the solution was 0.1 g/ml.

Preferably, the preparation method of the sulfuric acid aqueous solution of the double-distilled aniline in the step (1) comprises the following steps: 0.1mol/L redistilled aniline was dissolved in 0.1mol/L sulfuric acid aqueous solution of the same volume, and stirred at room temperature for 10 min.

Preferably, the ammonium persulfate solution in the step (1) is 0.1mol/L, and the ammonium persulfate and HAuCl are mixed₄Adding the mixture according to the molar weight ratio of (3-3.5): 1.

preferably, the mass ratio of the sulfonated polyether ether ketone to the gold palladium doped polyaniline nanocomposite material in the step (2) is (3.2-5): 1.

in conclusion, the beneficial effects of the invention are as follows: the gold-palladium doped polyaniline nano composite material prepared by the invention has outstanding inherent conductivity, excellent reaction catalysis performance and extremely strong metal corrosion resistance, can effectively improve the gas and liquid barrier performance of a polymer film, generates obvious interference on the movement of a polymer macromolecular chain, improves the mechanical stability and solvent resistance of the composite film, and can be widely applied to the field of fuel cell proton exchange membranes.

Detailed Description

The following further describes the embodiments of the present invention, which are not to be construed as limiting the invention.