Science China Materials

, Volume 62, Issue 2, pp 211–224 | Cite as

Densely quaternized anion exchange membranes synthesized from Ullmann coupling extension of ionic segments for vanadium redox flow batteries

  • Yu Chen (陈煜)
  • Qilang Lin (林起浪)
  • Yuying Zheng (郑玉婴)
  • Yan Yu (于岩)
  • Dongyang Chen (陈栋阳)Email author


Membranes with high ion conductivity and selectivity are important for vanadium redox flow batteries. Herein, densely quaternized anion exchange membranes based on quaternary ammonium functionalized octa-benzylmethyl-containing poly(fluorenyl ether ketone)s (QA-OMPFEKs) were prepared from the (i) condensation polymerization of a newly developed octa-benzylmethyl-containing bisphenol monomer via Ullmann coupling, (ii) bromination at the benzylmethyl sites using N-bromosuccinimide, and (iii) quaternization of the bromomethyl groups using trimethylamine. The QA-OMPFEK-20 with an ion exchange capacity (IEC) of 1.66 mmol g−1 exhibited a higher SO42− conductivity (9.62 mS cm−1) than that of the QA-TMPFEK-40 (4.82 mS cm−1) at room temperature, which had a slightly higher IEC of 1.73 mmol g−1 but much lower QA density. The enhanced SO42− conductivity of QA-OMPFEK-20 was attributed to the ion-segregated structure arising from the densely anchored QA groups, which was validated by SAXS observation. Furthermore, the QA-OMPFEK-20 showed much lower VO2+ permeability (1.24×10−14 m2 s−1) than QA-TMPFEK-40 (5.40×10−13 m2 s−1) and Nafion N212 (5.36×10−12 m2 s−1), leading to improved Coulombic and energy efficiencies in Vanadium redox flow batteries (VRFBs). Therefore, the Ullmann coupling extension is a valuable approach for the development of high performance anion exchange membranes for VRFBs.


anion exchange membranes quaternary ammonium poly(fluorenyl ether ketone)s Ullmann coupling extension phase separation 



离子传导率和选择性是全钒液流电池隔膜的两项核心性能指标. 本文基于乌尔曼偶联反应设计合成含八苯甲基的双酚单体, 然后依次将其聚合、 溴甲基化、 季铵化制得一系列密集季铵化型阴离子交换膜(QA-OMPFEKs). 产物QA-OMPFEK-20 (离子交换容量IEC=1.66 mmol g−1)的室温SO42−传导率为9.62 mS cm−1, 明显高于参照样品QA-TMPFEK-40 (IEC = 1.73 mmol g−1)的4.82 mS cm−1. 这归因于QA-OMPFEK-20经小角X射线散射所证实的离子聚集型结构. 此外, QA-OMPFEK-20的钒离子渗透率(1.24×10−14 m2 s−1)明显低于QA-TMPFEK-40 (5.40×10−13 m2 s−1)和Nafion N212 (5.36×10−12 m2 s−1), 从而使其全钒液流电池的库伦效率和能量效率最高. 可见, 乌尔曼偶联反应是合成高性能全钒液流电池阴离子交换膜的有效路径.



This work was supported by the National Natural Science Foundation of China (51503038).

Supplementary material

40843_2018_9299_MOESM1_ESM.pdf (672 kb)
Densely quaternized anion exchange membranes synthesized from Ullmann coupling extension of ionic segments for vanadium redox flow batteries


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Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Yu Chen (陈煜)
    • 1
  • Qilang Lin (林起浪)
    • 1
  • Yuying Zheng (郑玉婴)
    • 1
  • Yan Yu (于岩)
    • 1
    • 2
  • Dongyang Chen (陈栋阳)
    • 1
    • 2
    Email author
  1. 1.College of Materials Science and EngineeringFuzhou UniversityFuzhouChina
  2. 2.Key Laboratory of Eco-materials Advanced Technology (Fuzhou University)FuzhouChina

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