Research progress of the sulfonated poly(ether ether ketone)s membranes for proton exchange membrane fuel cell

doi:10.16085/j.issn.1000-6613.2016.09.029

Abstract

Abstract: The Nafion membrane generally used in proton exchange membrane fuel cell(PEMFC) possesses high proton conductivity,good thermal and chemical stability. However,its preparation cost is too high and its proton conductivity nearly decreases to zero at high temperature. This paper reviewed the progress of sulfonated poly(ether ether ketone) (SPEEK) and SPEEK/ionic liquid(IL) modified composite membrane as one of the Nafion alternative membrane. Two preparation methods of SPEEK classified by direct sulfonation method and sulfonated monomer polymerization method were also introduced. The direct sulfonation method was easy,however,the degree of sulfonation(DS) was less than 1.0 and the reaction was difficult to control. The sulfonated monomer polymerization method was difficult and its raw material was poisonous. However,DS can be easily controlled in this way. The effect of reaction time,temperature and ratio of raw materials,sulfonated monomer species, membrane preparation process and solvent on the performance of SPEEK was also overviewed and analyzed. It was found that in the direct sulfonation method the DS was negatively correlated with temperature and positively with the reaction time,while little relationship with the ratio of raw materials. In order to improve the performance of PEMFC,critical problems such as the loss of ionic liquids and the compatibility with Pt-based catalyst which resulted in lower battery performance during fuel cells operation should be solved in the future development of SPEEK/IL modified composite membranes.

Key words: SPEEK membrane, ionic liquids, loss, compatibility

摘要： Nafion膜具有优良的化学稳定性和导电性能，但是它成本高，高温下几乎不导电。本文回顾了Nafion替代膜之一——磺化聚醚醚酮（SPEEK）膜及SPEEK/离子液体（IL）复合膜的研究进展。介绍了SPEEK制备的两种方法：直接磺化法和磺化单体聚合法，其中直接磺化法工艺简单，但磺化度（DS）≤1.0，反应较难控制；磺化单体聚合法DS可控，但工艺复杂，原料有毒。简述了温度、反应时间、原料配比、磺化单体种类、制膜工艺及溶剂对SPEEK膜性能的影响：直接磺化法中DS与温度成负相关，与反应时间成正相关，与原料配比关系不大；磺化单体聚合法中DS受磺化单体的种类和氟酮与磺化氟酮的比例影响较大。着重介绍了SPEEK/咪唑离子液体复合膜和SPEEK/季铵盐离子液体复合膜的研究现状及应用于质子交换膜燃料电池（PEMFC）时存在的问题。最后对SPEEK/IL复合膜未来的研究方向进行了展望，即解决燃料电池运行过程中复合膜中离子液体流失及与Pt基催化剂相容性等关键问题，以提高PEMFC的性能。

关键词: 磺化聚醚醚酮膜, 离子液体, 流失, 相容性

CLC Number:

TM911.48

SUN Yuanyuan, QU Shuguo, LI Jianlong. Research progress of the sulfonated poly(ether ether ketone)s membranes for proton exchange membrane fuel cell[J]. Chemical Industry and Engineering Progree, 2016, 35(09): 2850-2860.

孙媛媛, 屈树国, 李建隆. 质子交换膜燃料电池用磺化聚醚醚酮膜的研究进展[J]. 化工进展, 2016, 35(09): 2850-2860.

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