Page 53 - 《精细化工》2022年第4期

第 39 卷第 4 期 精 细 化 工 Vol.39, No.4
2022 年 4 月 FINE CHEMICALS Apr. 2022

功能材料
一类含柔性侧链结构质子交换膜的制备与性能

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蔡世举，汪称意 ，钱佳锋，郑 慧，李 坚
（常州大学 材料科学与工程学院，江苏 常州 213164）

摘要：利用含侧甲基结构聚芳醚砜的溴化和接枝磺化反应，制备了一系列结构单元中含有 4 个柔性侧链结构的
磺化聚芳醚砜（4SPAES-x）{x=n〔3,3ʹ-二(3ʹʹ,5ʹʹ-二甲基苯基)-4,4ʹ-二氟二苯砜〕/n(4,4ʹ-二羟基联苯)×100}。通过
1 HNMR、GPC、AFM、电子万能试验机、TG 对其进行了结构表征和性能测试。将 4SPAES-x 膜用作钒液流电
池（VRFB）的质子交换膜，并对 VRFB 性能进行了评价。结果表明，所制备的 4SPAES-x 膜具有良好的亲水/
疏水相分离形态结构。4SPAES-x 膜的离子交换容量在 1.12~1.74 mmol/g 之间，30 ℃时的吸水率、溶胀率和质
子传导率分别为 11%~32%、7%~22%和 21~86 mS/cm，均随磺化比例的增大而增大。4SPAES-25 膜组装的钒液
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流单电池在 40 mA/cm 电流密度下能量效率最高为 83.3%，高于 Nafion 115 的 81.5%。此外，该单电池还具有良
好的循环稳定性。
关键词：质子交换膜；侧链磺化；能量效率；钒液流电池；功能材料
中图分类号：TQ323 文献标识码：A 文章编号：1003-5214 (2022) 04-0689-08

Preparation and properties of a class of proton exchange
membranes with flexible side chains

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CAI Shiju, WANG Chenyi , QIAN Jiafeng, ZHENG Hui, LI Jian
（School of Materials Science & Engineering, Changzhou University, Changzhou 213164, Jiangsu, China）

Abstract: A series of sulfonated poly(aryl ether sulfone)s (4SPAES-x) {x=n[3,3ʹ-bis(3ʹʹ, 5ʹʹ-dimethylphenyl)-
4,4ʹ-difluorobenzene sulfon]/n(4,4ʹ-dihydroxy biphenyl)×100} with four flexible side chains in repeated
units were prepared by bromination and graft sulfonation of poly(aryl ether sulfone) with side methyl
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structure. The chemical structure and properties of 4SPAES-x were characterized and tested by HNMR,
GPC, AFM, electronic universal testing machine and TG. The 4SPAES-x membranes were used as a proton
exchange membrane for vanadium redox flow battery (VRFB), and the performance of VRFB was
evaluated. The results showed that the prepared 4SPAES-x membranes had a good hydrophilic/hydrophobic
phase separation morphology. The ion exchange capacities of 4SPAES-x membranes were 1.12~1.74
mmol/g, and the water absorption, swelling rate and proton conductivity at 30 ℃ were 11%~32%, 7%~22% and
21~86 mS/cm, respectively, which increased with the increase of sulfonation ratio. The maximum energy
efficiency of the vanadium redox flow single battery assembled with 4SPAES-25 membrane was 83.3% at a
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current density of 40 mA/cm , higher than that of Nafion 115 (81.5%). In addition, the single battery had good
cycle stability.
Key words: proton exchange membrane; side chain sulfonation; energy efficiency; vanadium redox flow
battery; functional materials

近年来，全钒氧化还原液流电池（又称钒液流 广泛关注 [1-4] 。VRFB 主要由电极、电解液和离子交
电池，缩写为 VRFB）由于其响应速度快、存储容 换膜 3 个部分组成，其中离子交换膜是 VRFB 关键
量设计独立、使用寿命长和成本低等特性受到人们 组成部分，承担着分隔正负极电解液和进行离子传

收稿日期：2021-10-12; 定用日期：2021-12-20; DOI: 10.13550/j.jxhg.20211038
基金项目：江苏省研究生科研与实践创新计划项目（KYCX21_2803）；江苏省高校优势学科资助计划
作者简介：蔡世举（1996—），男，硕士生，E-mail：1185460244@qq.com。联系人：汪称意（1981—），男，教授，E-mail：wangcy@
cczu.edu.cn。