膜科学与技术

哌啶阳离子功能化侧链型阴离子交换膜的制备

作者：林陈晓卜俊杰刘芳华朱爱梅张秋根刘庆林

单位：厦门大学化学化工学院，厦门，361005

关键词：哌啶鎓盐；侧链型；阴离子交换膜；碱性燃料电池；

出版年,卷(期):页码： 2018,38(3):1-8

摘要：

摘要：燃料电池因其能量转化率高、污染小等特点，是当前的研究热点。然而，作为关键部件的阴离子交换膜仍然存在离子电导率低、耐碱性能差等缺点，这限制了燃料电池的发展。利用威廉姆森成醚反应在聚醚酮主链接枝哌啶鎓盐，成功制备了侧链型阴离子交换膜。设计的哌啶鎓盐通过长柔性亚甲基与主链相连，使膜内形成有利于高效离子传输的微相分离结构，PEK-CQA-1.0膜在80 oC的电导率高达72.7 mS·cm-1。此外，哌啶阳离子基团离主链较远，减弱了对主链的吸电子作用；同时，环型结构的哌啶阳离子具有一定的空间位阻，减少了OH-对阳离子基团的攻击，使膜表现出优异的耐碱性能。PEK-CQA-0.8膜在60 oC下1 M KOH水溶液中浸泡360 h后，离子电导率仅下降了8.8%，有望应用于碱性燃料电池。

Abstract: Fuel cells have become research hotpot due to their high efficiency and low pollution. As one of the core component of fuel cells, anion exchange membranes (AEMs) still face the dilemma of low conductivity and poor alkaline stability. Herein, side-chain-type anion exchange membranes are prepared by grafting piperidinium groups into poly(ether ketone)s backbone via Williamson reaction. The piperidinium groups are designed to connect the poly(ether ketone)s backbone via long alkyl spacers. As a result, all the AEMs demonstrate obvious microphase separated morphology in the membranes and

参考文献：

参考文献:
[1]       Zhang H W, Chen D Z, Xianze Y, et al. Anion‐Exchange Membranes for Fuel Cells: Synthesis Strategies, Properties and Perspectives[J]. Fuel Cells, 2015, 15(6): 761-780.
[2]       Merle G, Wessling M, Nijmeijer K. Anion exchange membranes for alkaline fuel cells: A review[J]. J Membr Sci, 2011, 377(1): 1-35.
[3]       Varcoe J R, Atanassov P, Dekel D R, et al. Anion-exchange membranes in electrochemical energy systems[J]. Energy Environ Sci, 2014, 7(10): 3135-3191.
[4]       林陈晓, 张秋根, 朱爱梅, 等. 燃料电池用阴离子交换膜：基于优化离子电导率的结构调控研究[J]. 膜科学与技术, 2015, 35(5): 102-108.
[5]       Li N, Yan T, Li Z, et al. Comb-shaped polymers to enhance hydroxide transport in anion exchange membranes[J]. Energy Environ Sci, 2012, 5(7): 7888-7892.
[6]       Li N, Leng Y, Hickner M A, et al. Highly stable, anion conductive, comb-shaped copolymers for alkaline fuel cells[J]. J Am Chem Soc, 2013, 135(27): 10124-10133.
[7]       Lin C X, Huang X L, Guo D, et al. Side-chain-type anion exchange membranes bearing pendant quaternary ammonium groups via flexible spacers for fuel cells[J]. J Mater Chem A, 2016, 4(36): 13938-13948.
[8]       Dang H S, Weiber E A, Jannasch P. Poly (phenylene oxide) functionalized with quaternary ammonium groups via flexible alkyl spacers for high-performance anion exchange membranes[J]. J Mater Chem A, 2015, 3(10): 5280-5284.
[9]       Zhuo Y Z, Lai A L, Zhang Q G, et al. Enhancement of hydroxide conductivity by grafting flexible pendant imidazolium groups into poly (arylene ether sulfone) as anion exchange membranes[J]. J Mater Chem A, 2015, 3(35): 18105-18114.
[10]    Lai A N, Wang L S, Lin C X, et al. Phenolphthalein-based poly (arylene ether sulfone nitrile) s multiblock copolymers as anion exchange membranes for alkaline fuel cells[J]. ACS Appl Mater Interfaces, 2015, 7(15): 8284-8292.
[11]    Shin D W, Guiver M D, Lee Y M. Hydrocarbon-Based Polymer Electrolyte Membranes: Importance of Morphology on Ion Transport and Membrane Stability[J]. Chem Rev, 2017, 117(6): 4759-4805.
[12]    Stamenkovic V R, Strmcnik D, Lopes P P, et al. Energy and fuels from electrochemical interfaces[J]. Nature Mater, 2017, 16(1): 57-69.
[13]    Marino M G, Kreuer K D. Alkaline stability of quaternary ammonium cations for alkaline fuel cell membranes and ionic liquids[J]. ChemSusChem, 2015, 8(3): 513-523.
[14]    Li N, Leng Y, Hickner M A, et al. Highly stable, anion conductive, comb-shaped copolymers for alkaline fuel cells[J]. J Am Chem Soc, 2013, 135(27): 10124-10133.
[15]    Chempath S, Einsla B R, Pratt L R, et al. Mechanism of tetraalkylammonium headgroup degradation in alkaline fuel cell membranes[J]. J Phys Chem C, 2008, 112(9): 3179-3182.
[16]    Zhang Z, Wu L, Varcoe J, et al. Aromatic polyelectrolytes via polyacylation of pre-quaternized monomers for alkaline fuel cells[J]. J Mater Chem A, 2013, 1(7): 2595-2601.
[17]    Mohanty A D, Tignor S E, Sturgeon M R, et al. Thermochemical Stability Study of Alkyl-Tethered Quaternary Ammonium Cations for Anion Exchange Membrane Fuel Cells[J]. J Electrochem Soc, 2017, 164(13): F1279-F1285.
[18]    Ponce-González J, Whelligan D K, Wang L, et al. High performance aliphatic-heterocyclic benzyl-quaternary ammonium radiation-grafted anion-exchange membranes[J]. Energy Environ Sci, 2016, 9(12): 3724-3735.
[19]    Zhang M, Liu J, Wang Y, et al. Highly stable anion exchange membranes based on quaternized polypropylene[J]. J Mater Chem A, 2015, 3(23): 12284-12296.
[20]    Zhu L, Pan J, Wang Y, et al. Multication side chain anion exchange membranes[J]. Macromolecules, 2016, 49(3): 815-824.

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