单离子聚合物电解质膜的制备及其结构表征与性能研究
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摘要
单离子聚合物电解质是指将阴离子(或阳离子)固定在聚合物主链上,仅有阳离子(或阴离子)发生迁移的聚合物电解质。目前商品化的单离子聚合物电解质是以Du Pont公司生产的Nafion?为代表的全氟磺酸型聚合物电解质,然而因其价格昂贵(800$/m2)不能得到广泛的应用,严重地制约了我国相关产业的发展。此外氟化合物的生产和应用会对环境造成很大的污染。本文正是以此为背景,旨在对碳氢骨架聚合物电解质的开发进行一次探索和尝试。
高压静电纺丝法所制备的聚合物无纺布是一种有纳米微孔的多孔材料,它具有很大的比表面积,在物理、化学性质方面表现出特异性,近年来已经应用于很多研究领域。但目前对单离子聚合物电解质的电纺在国内外还处于空白。本文对高压静电纺丝法在单离子聚合物电解质成膜方面的应用做了一次大胆的尝试,并对无纺布膜的性质进行研究。
本文以聚乙烯乙烯醇为基体树脂,利用其羟基的反应活性,通过威廉姆森反应将短链的聚乙二醇结构引入聚乙烯乙烯醇主链上,并通过磺酸丙内酯开环反应对其侧链进行磺化,制备出一种主链为疏水的聚乙烯链段,侧链为亚乙氧基结构,侧链末端为磺酸氢的梳形单离子聚合物电解质。通过对威廉姆森反应和磺酸丙内酯开环反应影响因素的研究,确定合成反应的工艺条件,并对反应中间体和最终产物的结构、分子量以及热学性质进行了表征。结果表明,所制得的单离子聚合物电解质侧链长度可控性较好,热学性质较为稳定。
首次将高压静电纺丝法应用于单离子聚合物电解质膜的制备,制得了单离子聚合物电解质无纺布膜。研究电纺丝工艺对无纺布膜微观形貌的影响,确定了纺丝工艺条件,比较了无纺布膜与铸膜的离子交换容量、吸水率、尺寸稳定性、力学性能、结晶性等性质。结果表明,侧链长度相同时,聚合物电解质无纺布膜的吸水率较高(室温下吸水率>200%),尺寸稳定性较好(室温下体积溶胀率<5%),且无纺布膜的吸水率对浸泡时间的依赖性较
Single ion electrolyte is a kind of polymer electrolyte in which only the cation or anion is mobile and the counter-ions is fixed onto the backbone of polymer electrolytes. The perfluorinated sulphonic acid cation exchange Nafion? membrane, manufactured by E.I. Du Pont de Nemoure and Co. in 1972, is the representative of commercially available single ion solid polymer electrolytes. However, in China, the high costs of Nafion? membranes bring about the limits for its application in related industries. And the production and application of fluorochemicals will severely pollute the environments as well. An effort was made to meet the needs of preparing a polymer electrolyte with hydrocarbon backbone in this paper.
The electrospun non-woven membrane is a kind of porous material with many nano poles. Because of the high specific surface area per unit mass, the non-woven membranes have showed its special physics and chemical performances in many potential applications. In the resent years, the electrospinning technique has been used in many kinds of polymer to obtain non-woven membranes. But the electrospinning of single ion polymer electrolyte has not been reported. In the paper, the polymer electrolyte non-woven membranes have been produced by electrospinning, and the relevant properties of the electrospun membranes have been studied.
The backbone of poly (ethylene-co-vinyl alcohol) (EVOH) has been grafted by poly (ethylene glycol) (PEG) through the Williamson reaction and the sulfonic groups have been introduced on the end of PEG side chain by the open ring
高压静电纺丝法所制备的聚合物无纺布是一种有纳米微孔的多孔材料,它具有很大的比表面积,在物理、化学性质方面表现出特异性,近年来已经应用于很多研究领域。但目前对单离子聚合物电解质的电纺在国内外还处于空白。本文对高压静电纺丝法在单离子聚合物电解质成膜方面的应用做了一次大胆的尝试,并对无纺布膜的性质进行研究。
本文以聚乙烯乙烯醇为基体树脂,利用其羟基的反应活性,通过威廉姆森反应将短链的聚乙二醇结构引入聚乙烯乙烯醇主链上,并通过磺酸丙内酯开环反应对其侧链进行磺化,制备出一种主链为疏水的聚乙烯链段,侧链为亚乙氧基结构,侧链末端为磺酸氢的梳形单离子聚合物电解质。通过对威廉姆森反应和磺酸丙内酯开环反应影响因素的研究,确定合成反应的工艺条件,并对反应中间体和最终产物的结构、分子量以及热学性质进行了表征。结果表明,所制得的单离子聚合物电解质侧链长度可控性较好,热学性质较为稳定。
首次将高压静电纺丝法应用于单离子聚合物电解质膜的制备,制得了单离子聚合物电解质无纺布膜。研究电纺丝工艺对无纺布膜微观形貌的影响,确定了纺丝工艺条件,比较了无纺布膜与铸膜的离子交换容量、吸水率、尺寸稳定性、力学性能、结晶性等性质。结果表明,侧链长度相同时,聚合物电解质无纺布膜的吸水率较高(室温下吸水率>200%),尺寸稳定性较好(室温下体积溶胀率<5%),且无纺布膜的吸水率对浸泡时间的依赖性较
Single ion electrolyte is a kind of polymer electrolyte in which only the cation or anion is mobile and the counter-ions is fixed onto the backbone of polymer electrolytes. The perfluorinated sulphonic acid cation exchange Nafion? membrane, manufactured by E.I. Du Pont de Nemoure and Co. in 1972, is the representative of commercially available single ion solid polymer electrolytes. However, in China, the high costs of Nafion? membranes bring about the limits for its application in related industries. And the production and application of fluorochemicals will severely pollute the environments as well. An effort was made to meet the needs of preparing a polymer electrolyte with hydrocarbon backbone in this paper.
The electrospun non-woven membrane is a kind of porous material with many nano poles. Because of the high specific surface area per unit mass, the non-woven membranes have showed its special physics and chemical performances in many potential applications. In the resent years, the electrospinning technique has been used in many kinds of polymer to obtain non-woven membranes. But the electrospinning of single ion polymer electrolyte has not been reported. In the paper, the polymer electrolyte non-woven membranes have been produced by electrospinning, and the relevant properties of the electrospun membranes have been studied.
The backbone of poly (ethylene-co-vinyl alcohol) (EVOH) has been grafted by poly (ethylene glycol) (PEG) through the Williamson reaction and the sulfonic groups have been introduced on the end of PEG side chain by the open ring
引文
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