燃料电池用阴离子交换膜分子结构研究进展

doi:10.16085/j.issn.1000-6613.2022-0692

摘要/Abstract

摘要：

阴离子交换膜（AEMs）作为燃料电池的核心部件，其发展得到了普遍关注。然而，AEMs中聚合物骨架和阳离子基团无序的直接相连的结构导致了膜在应用过程中存在离子电导率低、碱稳定性差和机械性能不足等问题，因此对连接二者的分子结构进行设计，开发综合性能优异的AEMs很有必要。本文介绍了AEMs选择性透过的基本机理，并从不同的分子结构出发，总结了近年来应用较为广泛的嵌段结构、接枝结构、交联结构、局部高密度结构以及由局部高密度结构与其他三种结构组成的复合结构AEMs的研究进展；从离子电导率、碱稳定性、机械性能以及吸水率等方面对AEMs的性能提升进行了归纳，重点关注AEMs离子电导率和吸水率的权衡问题，并从分子结构及其组合使用的角度对燃料电池用AEMs的未来发展方向进行了展望。

关键词: 阴离子交换膜, 离子电导率, 碱稳定性, 机械性能, 吸水率

Abstract:

The development of anion exchange membranes (AEMs), which are the core components of fuel cells, has received widespread attention. However, the disordered and directly connected structure of polymer skeleton and cationic groups in AEMs leads to the problems of low ionic conductivity, poor alkali stability and insufficient mechanical property in the application process of the membrane. Thus, it is necessary to design the molecular structure connecting the polymer skeleton and cationic groups and develop AEMs with excellent comprehensive performance. The basic mechanism of the selective permeation of AEMs was introduced, and the research progress of AEMs with different molecular structures, such as block structure, graft structure, cross-linked structure, partial high density structure and composite structure composed of partial high density structure and the other three kinds of structures, was reviewed. The performance improvement of AEMs was summarized from the aspects of ionic conductivity, alkali stability, mechanical property and water absorption, and the trade-off between ionic conductivity and water absorption of AEMs was focused on. Finally, the future development direction of fuel cell AEMs from the aspects of molecular structure and its combination was prospected.

Key words: anion exchange membranes, ionic conductivity, alkali stability, mechanical property, bibulous rate

中图分类号:

TQ425.23⁺6

张洪铭, 卢炯元, 王三反. 燃料电池用阴离子交换膜分子结构研究进展[J]. 化工进展, 2022, 41(S1): 318-330.

ZHANG Hongming, LU Jiongyuan, WANG Sanfan. Research progress on molecular structure of anion exchange membrane for fuel cells[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 318-330.

图/表 18

图1 QA-PES多嵌段共聚物的分子结构示意图[11]

图2 聚醚砜多嵌段共聚物的分子结构示意图[13]

图3 辐射接枝AEMs的分子结构示意图[17]

图4 接枝不同数量季铵基团AEMs的分子结构示意图[20]

表1 接枝不同数量季铵基团AEMs的参数和性能

AEMs	每个侧链上的季铵基团数量/个	20℃时离子电导率/mS·cm^-1	吸水率/%	溶胀率/%
CS-1	1	30	143	70
CS-2	2	35	100	43
CS-3	3	41	82	34
CS-4	4	60	70	27
CS-5	5	65	65	19
CS-6	6	64	62	18

图5 PAEN-TPP-0.35的分子结构和核磁氢谱示意图[22]

图6 TQPAEK的分子结构示意图[24]

图7 PAES-QDTPM-x分子结构示意图[26]

图8 QA-PAEKs分子结构示意图[27]

图9 交联型聚醚砜AEMs的合成路线示意图[28]

图10 双胍基交联结构示意图(a) [33]以及双功能交联聚芳醚酮AEMs的结构示意图(b) [34]

图11 PVI@CNT分子结构示意图[35]

图12 四季铵基团交联结构示意图(a)以及双季铵基团交联结构示意图(b) [36]

图13 二氧苯环上含有2、3、4个季铵基团的多嵌段-高密度聚芳醚砜共聚物分子结构示意图[37]

图14 接枝-局部高密度QACz-PAEK-x的合成路线示意图[38]

图15 具有柔性侧链的交联-局部高密度季铵聚芳醚砜分子结构示意图[39]

图16 交联-局部高密度膜的结构示意图[40]

图17 含酚酞的聚芳醚砜交联-高密度AEMs分子结构示意图和离子基团聚集过程示意图[41]

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