阅读说明：本技术 全氟磺酸/纳米氧化铝质子交换膜的制备方法 (Preparation method of perfluorosulfonic acid/nano-alumina proton exchange membrane ) 是由 冯章启 金飞 严珂 杜丽娟 李�瑞 袁旭 李通 吴方方 张海洋 于 2018-07-21 设计创作，主要内容包括：本发明公开了一种全氟磺酸/纳米氧化铝质子交换膜的制备方法。所述方法先将纳米氧化铝颗粒高度分散在乙醇和水的混合溶液中得到纳米氧化铝分散液,并将全氟磺酸树脂粉末溶解在乙醇和水的混合溶液中,并加入高分子量的聚氧化乙烯,然后将两种溶液混合均匀得到纺丝溶液,再通过静电纺丝技术,制备全氟磺酸/纳米氧化铝纳米纤维膜,最后将全氟磺酸/纳米氧化铝纳米纤维膜退火、稀硫酸处理质子化得到质子交换膜。本发明制备的复合膜比表面积大,具有较高的质子导电率,其质子导电率可达0.061s/cm,目前生产的质子交换膜提高约3～4倍。(The invention discloses a preparation method of perfluorinated sulfonic acid/nano-alumina proton exchange membranes, which comprises the steps of dispersing nano-alumina particles in a mixed solution of ethanol and water to obtain a nano-alumina dispersion liquid, dissolving perfluorinated sulfonic acid resin powder in the mixed solution of ethanol and water, adding high-molecular-weight polyethylene oxide, uniformly mixing the two solutions to obtain a spinning solution, preparing a perfluorinated sulfonic acid/nano-alumina nanofiber membrane by an electrostatic spinning technology, and finally annealing the perfluorinated sulfonic acid/nano-alumina nanofiber membrane and protonating the annealed perfluorinated sulfonic acid/nano-alumina nanofiber membrane by dilute sulfuric acid to obtain the proton exchange membrane.)

1. The preparation method of the perfluorosulfonic acid/nano-alumina proton exchange membrane is characterized by comprising the following specific steps of:

step 1, taking a mixed solution of ethanol and water as a solvent, dissolving perfluorinated sulfonic acid resin in the solvent, adding polyoxyethylene, adding a dispersion liquid of nano-alumina, stirring until the mixture is uniformly mixed, and removing bubbles to obtain an electrostatic spinning solution, wherein the concentration of the perfluorinated sulfonic acid resin is 0.1-0.12 g/mL, the polyoxyethylene accounts for 1-3% of the mass of the perfluorinated sulfonic acid resin, and the nano-alumina accounts for 1-5% of the mass of the perfluorinated sulfonic acid resin;

step 2, adopting an electrostatic spinning method, setting the voltage to be 8-10 kV, the receiving distance to be 5-8 cm, and the solution flow rate to be 0.1-0.4 ml/h to obtain the perfluorosulfonic acid/nano-alumina nanofiber membrane;

and 3, annealing the nanofiber membrane at 120-150 ℃, treating with dilute sulfuric acid with the concentration of 0.1-0.5 mol/L to protonate, washing with water, and drying to obtain the perfluorosulfonic acid/nano aluminum oxide proton exchange membrane.

2. The preparation method according to claim 1, wherein in the step 1, the volume ratio of ethanol to water in the solvent is 3: 1-4: 1.

3. The preparation method according to claim 1, wherein in step 1, the particle size of the nano alumina is 90 ± 10 nm.

4. The preparation method according to claim 1, wherein in the step 1, the stirring time is 2-3 hours, and the stirring temperature is 50-60 ℃.

5. The method according to claim 1, wherein in step 1, the concentration of the perfluorosulfonic acid resin is 0.1g/mL, the polyoxyethylene accounts for 2% by mass of the perfluorosulfonic acid resin, and the nano-alumina accounts for 3% by mass of the perfluorosulfonic acid resin.

6. The method of claim 1, wherein in step 2, the needle has an inner diameter of 0.47 mm.

7. The preparation method according to claim 1, wherein in the step 3, the drying temperature is 70-80 ℃ and the drying time is 12-24 hours.

Technical Field

The invention belongs to the technical field of proton exchange membrane material preparation, and relates to a preparation method of perfluorinated sulfonic acid/nano aluminum oxide proton exchange membranes.

Background

Electrospinning is an effective means for preparing organic and inorganic polymer nanofibers, and can be used for preparing composite superfine continuous fibers with diameters ranging from micron to nanometer.

The proton exchange membrane is a core component of a novel fuel cell, the electrolyte used by the proton exchange membrane is solid organic membranes, and the membranes can conduct protons under the humidification condition.

Most of the currently used proton exchange membranes are cast membranes such as the Nafion series membranes, Nafion-115 and Nafion-117(Hou H, Sun G, Wu Z, et al. zirconium phosphate/Nafion115composite membrane for high-concentration DMFC [ J ]. International journal of Hydrogen Energy,2008,33(13): 3402) 3409.) produced by DuPont, and the proton conduction rate is only 0.015 s/cm. The proton exchange membrane is used as a core component of the fuel cell, and the performance of the proton exchange membrane has an important influence on the fuel cell, so that the proton exchange membrane is required to have high proton conductivity, and also to ensure the chemical stability and the dimensional stability.

Disclosure of Invention

The invention aims to provide a preparation method of perfluorinated sulfonic acid/nano-alumina proton exchange membranes with high conductivity, and solves the problems of low conductivity and poor chemical stability in the use process of the existing proton exchange membranes.

The technical scheme for realizing the purpose of the invention is as follows:

the preparation method of the perfluorosulfonic acid/nano-alumina proton exchange membrane comprises the following specific steps:

step 1, taking a mixed solution of ethanol and water as a solvent, dissolving perfluorinated sulfonic acid resin in the solvent, adding polyoxyethylene, adding a dispersion liquid of nano-alumina, stirring until the mixture is uniformly mixed, and removing bubbles to obtain an electrostatic spinning solution, wherein the concentration of the perfluorinated sulfonic acid resin is 0.1-0.12 g/mL, the polyoxyethylene accounts for 1-3% of the mass of the perfluorinated sulfonic acid resin, and the nano-alumina accounts for 1-5% of the mass of the perfluorinated sulfonic acid resin;

step 2, adopting an electrostatic spinning method, setting the voltage to be 8-10 kV, the receiving distance to be 5-8 cm, and the solution flow rate to be 0.1-0.4 ml/h to obtain the perfluorosulfonic acid/nano-alumina nanofiber membrane;

and 3, annealing the nanofiber membrane at 120-150 ℃, treating with dilute sulfuric acid with the concentration of 0.1-0.5 mol/L to protonate, washing with water, and drying to obtain the perfluorosulfonic acid/nano aluminum oxide proton exchange membrane.

Preferably, in the step 1, the volume ratio of ethanol to water in the solvent is 3: 1-4: 1.

Preferably, in step 1, the particle size of the nano alumina is 90 ± 10 nm.

Preferably, in the step 1, the stirring time is 2-3 h, and the stirring temperature is 50-60 ℃.

Preferably, in step 1, the concentration of the perfluorosulfonic acid resin is 0.1g/mL, the polyoxyethylene accounts for 2% of the mass of the perfluorosulfonic acid resin, and the nano-alumina accounts for 3% of the mass of the perfluorosulfonic acid resin.

Preferably, in step 2, the inner diameter of the needle is 0.47 mm.

Preferably, in the step 3, the drying temperature is 70-80 ℃, and the drying time is 12-24 hours.

Compared with the prior art, the invention has the following advantages:

(1) the invention has simple process and easily obtained raw materials;

(2) the composite membrane prepared by the method has large specific surface area and higher proton conductivity, the proton conductivity of the composite membrane can reach 0.061s/cm, and the currently produced proton exchange membrane is improved by about 3-4 times;

(3) the prepared composite membrane has high water absorption rate, good chemical stability and high efficiency utilization rate.

Drawings

FIG. 1 is a scanning electron microscope image of the nanofiber composite membrane prepared by the present invention.

Fig. 2 is an electrochemical impedance diagram of the nanofiber membrane prepared by the present invention.

FIG. 3 is a cyclic voltammogram of the nanofiber proton exchange membrane prepared in the present invention.

Fig. 4 is a water absorption diagram of the nanofiber composite membrane prepared in the present invention.

Detailed Description

The invention is described in further detail with reference to specific embodiments and the attached drawing figures.