含唑环的磺化聚芳醚酮砜类质子交换膜的制备与性能研究

发布时间：2018-01-03 06:31

本文关键词：含唑环的磺化聚芳醚酮砜类质子交换膜的制备与性能研究　出处：《长春工业大学》2017年硕士论文　论文类型：学位论文

【摘要】：随着能源危机和环境污染日益加重,开发清洁高效无污染的新能源成为了世界各国科学研究的热点。质子交换膜燃料电池(Proton Exchange Membrane Fuel Cell,PEMFC),近年来被世界各国争相研究,是因其拥有启动迅速、操作便利、能量转换效率高和清洁无污染等优点。质子交换膜(PEM)作为PEMFC的关键部分,其性能的优劣关乎PEMFC的应用前景。如今,商业应用最为普及的PEM是美国杜邦独立研发的Nafion膜,其具有杰出的化学稳定性和质子传递性能,但同时由于其制备成本高、阻醇性能差且高温质子传导率下降明显等缺点限制了其进一步的推广应用。因此,开发一种可替代Nafion膜且综合性能优异的新型膜材料成为科研学者的主要攻克方向。其中,磺化聚芳醚酮砜类(SPAEKS)被认为是最有应用前景的新型膜材料之一,其本身拥有突出的机械性能和热稳定性,且价格相对低廉。但是与Nafion膜一样,该类膜的质子传导主要依赖磺酸基团,而当磺化度较高时易导致膜发生过度溶胀,尺寸稳定性、氧化稳定性、阻醇性能和机械性能大幅度下降,从而使其使用性能大打折扣。因此,对磺化聚芳醚酮砜类膜材料进行合理的改性和修饰,使其综合性能提高显得十分重要。本文首先制备了含三唑侧基的磺化聚芳醚酮砜膜(SPT),以接枝的方式引入了三唑基团,利用三唑基团同时作为质子给体与受体的特性,以及三唑基团与磺酸基团之间的相互作用,提供了新的质子跳跃点,使质子以跳跃机理进行传输,极大的改善了质子膜在高温和低相对湿度条件下的质子传导率。120oC时,SPT-4膜的质子传导率高达0.166 S cm~(-1),远比相同测试标准Nafion膜的质子传导率要高。为进一步增强膜的阻醇能力,我们向体系内引入有机硅氧烷材料,以三唑改性的γ-缩水甘油醚氧丙基三甲氧基硅烷(GT)为交联剂,通过溶胶-凝胶法成功制得三唑改性KH560/磺化聚芳醚酮砜交联膜(AMSP/GT)。实验结果表明,交联结构改善了膜的尺寸稳定性,同时抑制了甲醇的透过,60oC时,AMSP/GT-30的甲醇渗透系数仅为9.95×10~(-7) cm~2 s~(-1),这要比相同测试标准下Nafion膜的甲醇透过率小一个数量级。同时,三唑基团的存在,提高了膜在高温时的质子传输性能,120oC时,AMSP/GT-30的质子传导率可达0.106 S cm~(-1)。通过引入三唑基团和构建交联结构,本文成功制备了阻醇性能良好且高温质子传导率优异的新型质子交换膜材料。
[Abstract]:With the increasing energy crisis and environmental pollution. The development of clean, efficient and pollution-free new energy has become a hot spot of scientific research all over the world. Proton Exchange membrane fuel Cell (. Proton Exchange Membrane Fuel Cell. In recent years, PEMFC has been studied by many countries all over the world because of its rapid start-up and convenient operation. Proton exchange membrane (PEM) is a key part of PEMFC, and its performance is related to the application prospect of PEMFC. PEM, which is the most popular commercial application, is an independent Nafion membrane developed by DuPont, USA. It has excellent chemical stability and proton transfer performance, but at the same time because of its high cost of preparation. The poor performance of alcohol and the obvious decrease of proton conductivity at high temperature limit its further application. The development of a new membrane material which can replace Nafion membrane and has excellent comprehensive properties has become the main research direction of researchers. Sulfonated poly (aryl ether ketone sulfone) (SPAEKS) is considered as one of the most promising novel membrane materials with outstanding mechanical properties and thermal stability. And the price is relatively low, but like Nafion membrane, the proton conduction of this kind of membrane mainly depends on the sulfonic group, but when the sulfonation degree is high, the membrane is prone to excessive swelling, dimensional stability, oxidation stability. The properties of alcohol resistance and mechanical properties were greatly reduced, so the performance of sulfonated poly (aryl ether ketone sulfone) membrane was modified and modified reasonably. It is very important to improve its comprehensive properties. Firstly, the sulfonated poly (aryl ether ketone sulfone) membrane SPT was prepared, and the triazole group was introduced by grafting. Using the properties of triazole group as a proton donor and acceptor, and the interaction between triazole group and sulfonic group, a new proton hopping point is provided, which makes the proton transport by jumping mechanism. The proton conductivities of SPT-4 membrane at high temperature and low relative humidity were greatly improved. The proton conductivity of SPT-4 membrane was as high as 0.166s / cm ~ (-1) under high temperature and low relative humidity. The proton conductivity of the Nafion membrane is much higher than that of the same test standard. In order to further enhance the alcohol resistance of the membrane, we introduced the organic siloxane material into the system. Triazole modified 纬 -glycidyl ether oxypropyl trimethoxysilane (GTZ) was used as crosslinking agent. Triazole modified KH560 / sulfonated poly (aryl ether ketone sulfone) crosslinked membrane was successfully prepared by sol-gel method. The experimental results showed that the crosslinking structure improved the dimensional stability of the membrane. At 60oC, the methanol permeability coefficient of AMSP / GT-30 was only 9.95 脳 10 ~ (-7) cm~2 ~ (-1). This is an order of magnitude less than the methanol transmittance of Nafion membrane under the same test standard. At the same time, the existence of triazole groups improves the proton transport performance of the membrane at 120oC at high temperature. The proton conductivity of AMSP/GT-30 can reach 0.106s / cm ~ (-1). The triazole group was introduced and the cross-linking structure was constructed. In this paper, a novel proton exchange membrane material with good alcohol resistance and high temperature proton conductivity was successfully prepared.
【学位授予单位】：长春工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.2;TM911.4

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