含氨基磺化聚芳醚酮砜类及其复合型质子交换膜的制备与性能研究

发布时间：2018-04-06 05:28

  本文选题：质子交换膜燃料电池　切入点：质子交换膜　出处：《长春工业大学》2017年硕士论文

【摘要】：质子交换膜燃料电池(PEMFC)作为一种新型产能材料,具有燃料利用率高,可以同时提供动能和热能,以及方便运输和环境友好等特点。作为该电池的核心部件,质子交换膜(PEM)不但能隔绝甲醇和氧化剂以确保燃料电池的正常使用,而且可以作为质子的有效传输载体,使得质子可以在燃料电池中有效的进行传输,保证燃料电池可以正常、稳定、高效的工作。当前已经商品化的Nafion系列质子交换膜在质子传导率方面具有较好的表现,不过在高温操作环境下,燃料(甲醇)透过率过高,质子传导率下降过快是该型质子交换膜的主要问题。本文针对这两种问题制备了两种聚合物膜,从两个方面对这些问题进行改善。通过溶液共混法制备氨基磺化聚芳醚酮砜(Am-SPAEKS)和聚乙烯醇(PVA)的杂化膜。改变PVA的组分含量,制成不同配比的Am-SPAEKS/PVA复合膜,通过FT-IR测试证明了复合膜的成功制备,同时对复合膜的其他性能也进行了比较全面的测试。在复合膜中,氨基与磺酸基团的氢键作用以及羟基与磺酸基团间的酸碱离子对作用保证了复合膜的稳定性。与纯Am-SPAEKS质子交换膜相比较来说,其阻醇性能有明显的提高,在25℃时,Am-SPAEKS/PVA50%的甲醇渗透率数值仅为2.95×10-7cm2 s-1,而在60℃时,其甲醇渗透率为8.26×10-7 cm2 s-1。另外,我们制备了新型双氨基双酚单体(2,4-二氨基苯基对苯二酚(2Am-PHQ)),并且通过缩聚反应,控制氨基双酚单体与双酚A的比例,合成不同配比的新型双氨基磺化聚芳醚酮砜聚合物(2Am-SPAEKS)。利用氨基和磺酸基团之间的酸碱离子对作用,一定程度上保证聚合物膜在吸水的过程中溶胀度不会过大,保证聚合物膜具有良好的机械性能以及尺寸稳定性。同时由于氨基含量的增大,高温时质子通过“Grotthuss”机理进行传输的通道增多,改善了高温时质子交换膜的质子传导率。当氨基含量在40%的时候,100℃时聚合物膜的质子传导率依然能达到0.095 S cm-1。在质子交换膜燃料电池膜材料的应用方面具有很大的应用前景。
[Abstract]:Proton exchange membrane fuel cell (PEMFC) is a new type of material with high fuel efficiency, which can provide both kinetic energy and heat energy, as well as facilitate transportation and environmental friendliness.As a core component of the cell, PEM not only insulates methanol and oxidants to ensure the normal use of fuel cells, but also acts as an effective transport carrier of protons, enabling protons to be efficiently transported in fuel cells.Ensure that the fuel cell can work normally, stably and efficiently.The current commercial Nafion series of proton exchange membranes have a good performance in proton conductivity, but in the high temperature operating environment, the fuel (methanol) transmission rate is too high.The main problem of this type of proton exchange membrane is that the proton conductivity decreases too fast.In this paper, two kinds of polymer membranes were prepared to solve these two problems.The hybrid membranes of am-SPAEKS and PVA were prepared by solution blending.The Am-SPAEKS/PVA composite membrane with different ratio was made by changing the composition of PVA. The FT-IR test proved that the composite membrane was successfully prepared, and the other properties of the composite membrane were also tested comprehensively.The stability of the composite membrane is ensured by the hydrogen bonding between amino and sulfonic groups and the interaction of acid and base ion pairs between hydroxyl and sulfonic groups.Compared with the pure Am-SPAEKS proton exchange membrane, the alcohol resistance performance of the membrane is obviously improved. The methanol permeability of 50% Am-SPAEKS / PVA is only 2.95 脳 10-7cm2 s-1 at 25 鈩，

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