储能科学与技术 ›› 2018, Vol. 7 ›› Issue (1): 66-.doi: 10.12028/j.issn.2095-4239.2017.0148

• 研究及进展 • 上一篇    下一篇

高质子选择性的SPEEK/SGO质子交换膜制备及钒电池应用

刘金宇，李丹，王丽华，韩旭彤，黄庆林   

  1. 1天津工业大学材料科学与工程学院，天津 300387；2中国科学院化学研究所，北京 100190；3省部共建分离膜与膜过程国家重点实验室，天津 300387
  • 收稿日期:2017-09-19 修回日期:2017-11-02 出版日期:2018-01-01 发布日期:2018-01-01
  • 通讯作者: 王丽华，副研究员，E-mail：wanglh@iccas.ac.cn；韩旭彤，副研究员，E-mail：hanxutong@tjpu. edu.cn；黄庆林，副教授，E-mail：huangqinglin@tjpu.edu.cn。
  • 作者简介:刘金宇（1991—），男，硕士研究生，研究方向为质子交换膜制备及应用，E-mail：liujinyu5@163.com
  • 基金资助:
    国家自然科学基金项目（21376253），省部共建分离膜与膜过程国家重点实验室（天津工业大学）开放课题（M2-201502，15PTSYJC00250）

SPEEK/ SGO proton exchange membranes with superior proton selectivity for vanadium redox battery

LIU Jinyu, LI Dan, WANG Lihua, HAN Xutong, HUANG Qinglin   

  1. 1 School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, China; 2 Institute of Chemistry, Chinese Academy of Science, Beijing 100190, China; 3 State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin 300387, China
  • Received:2017-09-19 Revised:2017-11-02 Online:2018-01-01 Published:2018-01-01

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摘要：

质子交换膜作为钒液流电池的关键材料之一，其质子选择性决定钒电池的最终性能。本文对氧化石墨烯（GO）进行磺化改性得到其衍生物GO-SO3H（SGO），以SPEEK为基质，通过掺杂方式制备一系列质子交换膜（SPEEK/SGO，简写为S/SGO），对膜的含水率、离子交换容量、面电阻、质子电导率、钒离子渗透率、力学性能以及耐氧化性进行表征，并研究不同SGO含量共混膜的相关电池性能。SEM显示SGO在SPEEK基质中可较好分散，并且，SGO的加入提高了吸水率和质子电导率，S/SGO-1膜的质子选择性[14.14×104 (S·min)/cm3]比SPEEK膜[8.49×104 (S·min)/cm3]提高了66.5%。在50 mA/cm2电流密度下电池性能测试中，S/SGO-1膜的能量效率达到87.8%，自放电时间可达78 h，是Nafion115膜（30 h）的2.6倍。

关键词: 全钒液流电池, 磺化聚醚醚酮, 磺化氧化石墨烯, 离子选择性, 电池效率

Abstract:

 A series of novel ion exchange membranes (IEM), based on sulfonated poly (ether ether ketone) (SPEEK) with different weight ratios of sulfonated graphene oxide (SGO) loadings, were employed and investigated in vanadium redox flow battery (VRB). SPEEK was obtained by sulfonation of poly (ether ether ketone) (PEEK) in concentrated H2SO4, SGO is fabricated by grafting sulfonic groups to GO via a facile method. SPEEK/SGO membranes were prepared by solution casting method. GO and SGO were characterized by Fourier transform infrared spectroscopy (FT-IR) and the physicochemical properties of all membranes were measured by water uptake (WU), ion exchange capacity (IEC), proton conductivity, vanadium ion permeability, mechanical properties, oxidation stability and single cell performance. The result of FT-IR indicated that –SO3H groups were successfully grafted to GO, SEM images revealed the good dispersion of SGO in the SPEEK matrix. And other results showed that added SGO increased the WU and proton conductivity of composite membranes, the proton selectivity of S/SGO-1 membrane (14.14×104 S·min·cm3) was 66.5% higher than that of SPEEK (8.49×104 S·min·cm3). In single cell test, VRB with S/SGO-1 showed coulombic efficiency (CE) of 95.5%, VE of 92.0% and EE of 87.8% with good cycle stability, and the self-discharge time of VRB with S/SGO-1 membrane (78 h) is longer than that of Nafion115 (30 h). All experimental results indicate that incorporation of SGO can reduce the vanadium permeability and maintain high VE of SPEEK at the same time. S/SGO IEMs, especially S/SGO-1 shows promising prospects for VRB.

Key words: vanadium redox flow battery, sulfonated poly (ether ether ketone), sulfonated graphene oxide, proton selectivity, cell efficiency