磺化聚砜-聚多巴胺-ZrO2有机无机杂化复合质子交换膜的结构及性能

Structure and properties of sulfonated polysulfone-poly-dopamine-ZrO2 hybrid composite proton exchange membrane

  • 摘要: 为了解决燃料电池质子交换膜在高温全水合状态下的质子传导率低、易溶胀的问题,以商用磺化聚砜(PSF)多孔膜为基体,经聚多巴胺(PDA)表面沉积修饰后,在膜表面矿化形成ZrO2层从而制备PSF-PDA-ZrO2复合质子交换膜。研究了PDA沉积条件和ZrO2矿化工艺对PSF-PDA-ZrO2复合膜表面微观形貌及元素分布的影响规律;选择PDA沉积时间为5 h的PSF-PDA改性膜进行矿化,随矿化时间的增加,其表面矿化层Zr元素含量显著提高。对PSF-PDA-ZrO2复合膜进行吸水率、溶胀率和电导率进行测试。结果表明,相较于PSF多孔膜,ZrO2矿化层显著抑制了PSF-PDA-ZrO2复合膜在高温下的溶胀行为,其溶胀率随矿化时间的增加逐渐降低。PDA沉积时间为5 h,矿化时间分别为1 h、5 h、12 h和24 h的PSF-PDA-ZrO2复合膜质子传导率均高于纯PSF多孔膜,且随着矿化时间的增加复合膜的电导率逐渐降低。其中PDA沉积时间为5 h,矿化时间为1 h的PSF-PDA-ZrO2复合膜电导率在90℃时高达0.117 Scm-1,是同条件下纯PSF多孔膜的2.5倍。

     

    Abstract: The main obstacle of wide commercialization of proton exchange membrane is to maintain the high conductivity and low swelling ratio of proton exchange membrane at higher temperature under fully hydrated state. In order to solve this issue, by using poly-dopamine (PDA) as an intermediate layer, ZrO2 was formed on the commercial sulfonated polysulfone (PSF) porous membrane matrix, a facial approach of preparing well performed composite proton exchange membrane was proposed. The influence of PDA deposition conditions and ZrO2 mineralization process on the surface morphology and element distribution of PSF-PDA-ZrO2 composite membrane were investigated. The PSF-PDA modified membrane with PDA deposition time of 5 h was selected for mineralization. It is found that the content of Zr element on the surface mineralized layer of PSF-PDA-ZrO2 composite membranes is significantly increased with increasing mineralization time. The water uptake, swelling ratio and proton conductivity of PSF-PDA-ZrO2 composite membrane were tested. The results show that the surface of ZrO2 mineralized layer significantly inhibits the swelling ratio of PSF-PDA-ZrO2 composite membranes at higher temperature compared with PSF porous membranes, and the swelling ratio of composite membranes gradually reduces with the increase of ZrO2 mineralization time. The proton conductivity of PSF-PDA-ZrO2 composite membranes with mineralization time for 1 h, 5 h, 12 h and 24 h is higher than that of the pure PSF porous membrane, and the conductivity of the PSF-PDA-ZrO2 composite membranes decreases gradually with the increase of mineralization time. The proton conductivity of PSF-PDA-ZrO2 composite membrane after PDA deposition for 5 h and mineralization for 1 h is up to 0.117 Scm-1 at 90℃, which is 2.5 times of the PSF porous basement membrane.

     

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