侧链型磺化聚芳醚酮Nafion改性剂的制备及Nafion复合膜的性能研究

发布时间：2018-12-27 12:42

【摘要】：通过调节聚合物主体中亲水性的侧链磺烷基结构与疏水性的全芳主链结构间的比例,制备了主链重复单元结构中仅含单个萘基基团的不同磺化度的侧链磺烷基萘基聚芳醚酮质子交换膜材料(SNPAEK-xx),其中,磺化度高于1.30的SNPAEK-xx膜展现出优异的质子传导性能,80 oC时的质子传导率值高于0.145S cm-1,最高质子传导率值高达0.191 S cm-1,明显优于相同条件下的Nafion膜的质子传导性能。基于不同磺化度的SNPAEK-xx聚合物,展开了侧链磺烷基结构萘基聚芳醚酮质子交换膜材料的性能研究。质子交换膜材料中,平面萘基基团特有的基团间的相互作用有助于疏水相区的聚集形成,进而有利于形成更加明显的亲疏水相区分离结构,此外,分子链间萘基基团间的相互作用还有助于提高膜材料的化学稳定性,增强膜材料的机械性能,降低膜材料的吸水性能,基于平面萘基基团的特殊作用,进一步制备了主链重复单元结构中含有两个萘基基团的不同磺化度的双萘基聚芳醚酮质子交换膜材料(SDN-PAEK-x),双萘基基团的引入,极大的提高了质子交换膜材料的质子传导率,电池性能结果显示,含双萘基结构的SDN-PAEK-1.94质子交换膜材料具有显著优于Nafion膜的电池性能,40 oC时的最大功率密度可达32 m W·cm~(-2),明显优于Nafion膜80 oC条件下24 m W·cm~(-2)的最大功率密度,同时SDN-PAEK-1.94膜80 oC条件下的最大功率密度达到了60 m W·cm~(-2),明显优于相同条件下的Nafion膜的最大功率密度,可作为潜在的质子交换膜材料应用于直接甲醇燃料电池。考虑到制备的聚合物分子链中重复单元结构中含单个萘基基团的SNPAEK-xx与含双萘基基团的SDN-PAEK-x磺化聚合物间的综合性能差异和制备成本双重因素,我们首先选用综合性能优良,成本相对较低的SNPAEK-1.35作为Nafion改性剂与Nafion复合,制备一系列不同SNPAEK-1.35聚合物质量含量的Nafion/SNPAEK-x复合膜,探究SNPAEK-1.35Nafion改性剂的引入对Nafion膜综合性能的影响,研究结果显示,Nafion复合膜中SNPAEK-1.35聚合物改性剂的引入具有提高Nafion膜质子传导性能、阻醇性能和甲醇体系下电池性能的作用,同时Nafion膜的其它性能也获得了一定程度上的改善提高。
[Abstract]:By adjusting the ratio of the hydrophilic side chain sulfonyl structure to the hydrophobic all aromatic main chain structure in the polymer body, A side chain sulfonyl poly (aryl ether ketone) proton exchange membrane (SNPAEK-xx) with only a single naphthyl group in the main chain repeat unit structure was prepared, in which the side chain sulfonyl naphthalene polyaryl ether ketone proton exchange membrane (SNPAEK-xx) was prepared. The SNPAEK-xx membrane with sulfonation degree higher than 1.30 showed excellent proton conductivity. At 80 oC, the proton conductivity was higher than 0.145S cm-1, and the maximum proton conductivity was up to 0.191 S cm-1,. The proton conductivity of Nafion membrane is better than that of Nafion membrane under the same conditions. Based on SNPAEK-xx polymers with different sulfonation degrees, the properties of side chain sulfonyl naphthyl poly (aryl ether ketone) proton exchange membrane materials were studied. In the proton exchange membrane materials, the interaction between the unique groups of planar naphthyl groups is helpful to the aggregation of hydrophobic phase regions, and thus to the formation of more obvious hydrophilic phase separation structures. The interaction of naphthyl groups among molecular chains can also improve the chemical stability of the membrane materials, enhance the mechanical properties of the membrane materials, and reduce the water absorbency of the membrane materials, based on the special action of the planar naphthyl groups. The bisnaphthyl poly (aryl ether ketone) proton exchange membrane (SDN-PAEK-x) containing two naphthyl groups in the main chain repeat unit structure was further prepared. The proton conductivity of the proton exchange membrane material was greatly improved. The results of the battery performance showed that the SDN-PAEK-1.94 proton exchange membrane material with binaphthyl structure had significantly better performance than that of the Nafion membrane. The maximum power density at 40 oC can reach 32 MW cm~ (-2), which is obviously superior to the maximum power density of 24 MW cm~ (-2) at 80 oC of Nafion film. At the same time, the maximum power density of SDN-PAEK-1.94 film at 80 oC is 60 MW cm~ (-2), which is obviously better than that of Nafion film under the same condition. It can be used as a potential proton exchange membrane material for direct methanol fuel cells. Taking into account the difference in comprehensive properties and the cost of preparation of SNPAEK-xx with a single naphthyl group and SDN-PAEK-x sulfonated polymer with a bisnaphthyl group in the repetitive unit structure of the prepared polymer chain, Firstly, a series of Nafion/SNPAEK-x composite membranes with different mass content of SNPAEK-1.35 polymers were prepared by using SNPAEK-1.35, which has good comprehensive properties and relatively low cost, as Nafion modifier and Nafion. The effect of SNPAEK-1.35Nafion modifier on the comprehensive properties of Nafion membrane was investigated. The results showed that the introduction of SNPAEK-1.35 polymer modifier in Nafion composite membrane could improve the proton conductivity of Nafion membrane. The effects of alcohol resistance and cell performance in methanol system and other properties of Nafion film were improved to some extent.
【学位授予单位】：吉林大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ425.236

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