磺化聚醚醚酮基两性离子交换膜制备及在铁-铬液流电池中的应用

doi:10.19799/j.cnki.2095-4239.2021.0050

储能科学与技术 ›› 2021, Vol. 10 ›› Issue (4): 1305-1310.doi: 10.19799/j.cnki.2095-4239.2021.0050

磺化聚醚醚酮基两性离子交换膜制备及在铁-铬液流电池中的应用

张蓉¹(), 王曙光¹(), 孙璇¹, 江小松¹, 胡磊², 焉晓明², 贺高红²

^1.国家电投集团科学技术研究院有限公司，北京 102209
^2.大连理工大学，辽宁大连 116024

收稿日期:2021-02-02 修回日期:2021-02-27 出版日期:2021-07-05 发布日期:2021-06-25
通讯作者: 王曙光 E-mail:zhangrong@spic.com.cn;wangshuguang@spic.com.cn
作者简介:张蓉（1987—），女，硕士，工程师，主要研究方向为膜科学与技术，E-mail：zhangrong@spic.com.cn。
基金资助:
基?金?项?目?：基金项目:北京市科技计划项目(Z191100004619008);国家电投集团科学技术研究院有限公司B类课题(B-ZY05-201802)

Preparation of sulfonated poly（ether ether ketone） amphoteric ion exchange membrane and its application in iron-chromium redox flow battery

Rong ZHANG¹(), Shuguang WANG¹(), Xuan SUN¹, Xiaosong JIANG¹, Lei HU², Xiaoming YAN², Gaohong HE²

^1.State Power Investment Corporation Research Institute, Beijing 102209, China
^2.Dalian University of Technology, Dalian 116024, Liaoning, China

Received:2021-02-02 Revised:2021-02-27 Online:2021-07-05 Published:2021-06-25
Contact: Shuguang WANG E-mail:zhangrong@spic.com.cn;wangshuguang@spic.com.cn

摘要/Abstract

摘要：

针对铁-铬液流电池用的离子交换膜需求，通过在磺化聚醚醚酮(SPEEK)中引入了高亲水性聚乙烯亚胺(PEI)构建离子交联形成高效氢键网络，制备了两性离子交换膜(SPEEK/PEI)。通过引入胺基来构建离子交联结构，有效降低了SPEEK膜的溶胀度，抑制了铁-铬离子渗透；同时膜中亲水的PEI促进了亲水通道的形成，保持了高质子传导率。基于膜中高效氢键网络，SPEEK/PEI膜实现了铁-铬液流电池库仑效率与能量效率的有效提升。在70 mA/cm²电流密度下铁-铬液流电池性能测试中，SPEEK/PEI 3%膜的库仑效率为96.5%，能量效率达到79.4%。

关键词: 铁铬液流电池, 离子选择性, 磺化聚醚醚酮, 聚乙烯亚胺, 膜

Abstract:

An amphoteric ion-exchange membrane (SPEEK/PEI) was prepared in accordance with the demand for the Fe-Cr redox flow battery. An efficient hydrogen bond network was formed by introducing highly hydrophilic polyethyleneimine (PEI) into poly(ether ether ketone) (SPEEK). By introducing PEI with an amino group, the swelling ratio of the SPEEK membrane was effectively reduced, and the permeability of Fe²⁺ and Cr³⁺was inhibited. Furthermore, high proton conductivity was maintained owing to the formation of hydrophilic channels by PEI. Based on the efficient hydrogen bonding network, SPEEK/PEI membranes can effectively improve the Coulombic efficiency and energy efficiency of Fe-Cr redox flow batteries. The Coulombic efficiency of a 3% SPEEK/PEI membrane was 96.5%, and energy efficiency was 79.4% in the performance testing of the Fe-Cr redox flow battery at an ampere density of 70 mA/cm².

Key words: iron-chromium redox flow battery, ion selectivity, sulfonated poly(ether ether ketone), polyacetimide, membrane

中图分类号:

TM 912

张蓉, 王曙光, 孙璇, 江小松, 胡磊, 焉晓明, 贺高红. 磺化聚醚醚酮基两性离子交换膜制备及在铁-铬液流电池中的应用[J]. 储能科学与技术, 2021, 10(4): 1305-1310.

Rong ZHANG, Shuguang WANG, Xuan SUN, Xiaosong JIANG, Lei HU, Xiaoming YAN, Gaohong HE. Preparation of sulfonated poly（ether ether ketone） amphoteric ion exchange membrane and its application in iron-chromium redox flow battery[J]. Energy Storage Science and Technology, 2021, 10(4): 1305-1310.

图/表 7

图1

图2

表1

图3

图4

图5

图6

参考文献 29

1	杨林, 王含, 李晓蒙, 等. 铁-铬液流电池250 kW/1.5 MW·h示范电站建设案例分析[J]. 储能科学与技术, 2020, 9(3): 751-756.
	YANG L, WANG H, LI X M, et al. Introduction and engineering case analysis of 250 kW/1.5 MW·h iron-chromium redox flow batteries energy storage demonstration power station[J]. Energy Storage Science and Technology, 2020, 9(3): 751-756.
2	DING Y, ZHANG C K, ZHANG L Y, et al. Molecular engineering of organic electroactive materials for redox flow batteries[J]. Chemical Society Reviews, 2018, 47(1): 69-103.
3	ZHANG C K, ZHANG L Y, DING Y, et al. Progress and prospects of next-generation redox flow batteries[J]. Energy Storage Materials, 2018, 15: 324-350.
4	ZHANG C K, NIU Z H, PENG S S, et al. Phenothiazine-based organic catholyte for high-capacity and long-life aqueous redox flow batteries[J]. Advanced Materials, 2019, 31(24): 1901052.
5	胡磊, 高莉, 焉晓明, 等. 全钒液流电池膜离子选择性传导通道构建的研究进展[J]. 化工进展, 2020, 39(6): 2079-2092.
	HU L, GAO L, YAN X M, et al. Progress in construction of ion-selective transport channels in membranes for vanadium flow batteries[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2079-2092.
6	JIANG B, WU L T, YU L H, et al. A comparative study of Nafion series membranes for vanadium redox flow batteries[J]. Journal Membrane Science, 2016, 510: 18-26.
7	YE J Y, ZHAO X L, MA Y L, et al. Hybrid membranes dispersed with superhydrophilic TiO₂ nanotubes toward ultra‐stable and high-performance vanadium redox flow batteries[J]. Advanced Energy Materials, 2020, 10(22): 1904041.
8	ZHANG B G, ZHANG S H, WENG Z H, et al. Quaternized adamantane-containing poly(aryl ether ketone) anion exchange membranes for vanadium redox flow battery applications[J]. Journal of Power Sources, 2016, 325: 801-807.
9	ZHANG B G, WANG Q, GUAN S S, et al. High performance membranes based on new 2-adamantane containing poly(aryl ether ketone) for vanadium redox flow battery applications[J]. Journal of Power Sources, 2018, 399: 18-25.
10	DING Liming, SONG Xipeng, WANG Lihua, ZHAO Zhiping. Enhancing proton conductivity of polybenzimidazole membranes by introducing sulfonate for vanadium redox flow batteries applications[J]. Journal Membrane Science, 2019, 578: 126-135.
11	CHEN Y N, ZHANG S H, JIN J Y, et al. Poly(phthalazinone ether ketone) amphoteric ion exchange membranes with low water transport and vanadium permeability for vanadium redox flow battery application[J]. ACS Applied Energy Materials 2019, 2(11): 8207-8218.
12	CHEN Y N, ZHANG S H, LIU Q, et al. Investigation of poly(phthalazinone ether ketone) amphoteric ion exchange membranes in vanadium redox flow batteries[J]. Journal of Materials Science, 2020, 55(28): 13964-13979.
13	YANG P, LONG J, XUAN S S, et al. Branched sulfonated polyimide membrane with ionic cross-linking for vanadium redox flow battery application[J]. Journal of Power Sources, 2019: 438: 226993.
14	HUANG X D, PU Y, ZHOU Y Q, et al. In-situ and ex-situ degradation of sulfonated polyimide membrane for vanadium redox flow battery application[J]. Journal Membrane Science, 2017, 526: 281-292.
15	LU W J, YUAN Z Z, ZHAO Y Y, et al. High-performance porous uncharged membranes for vanadium flow battery applications created by tuning cohesive and swelling forces[J]. Energy & Environmental Science, 2016, 9(7): 2319-2325.
16	ZHANG Y X, ZHENG L Y, LIU B, et al. Sulfonated polysulfone proton exchange membrane influenced by a varied sulfonation degree for vanadium redox flow battery[J]. Journal Membrane Science, 2019, 584: 173-180.
17	DAI W J, SHEN Y, LI Z H, et al. SPEEK/graphene oxide nanocomposite membranes with superior cyclability for highly efficient vanadium redox flow battery[J]. Journal of Materials Chemistry A, 2014, 2(31): 12423-12432.
18	ZHANG Y X, WANG H X, LIU B, et al. An ultra-high ion selective hybrid proton exchange membrane incorporated with zwitterion-decorated graphene oxide for vanadium redox flow batteries[J]. Journal of Materials Chemistry A, 2019, 7(20): 12669-12680.
19	YUAN Z Z, LI X F, HU J B, et al. Degradation mechanism of sulfonated poly(ether ether ketone) (SPEEK) ion exchange membranes under vanadium flow battery medium[J]. Physical Chemistry Chemical Physics, 2014, 16(37): 19841-19847.
20	JIANG B W, HU L, YAN X M, et al. A new long-side-chain sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) /polybenzimidazole (PBI) amphoteric membrane for vanadium redox flow battery[J]. Chinese Journal of Chemical Engineering, 2020, 28(7): 1918-1924.
21	CHEN Y, LIU Z C, LIN M J, et al. Selectivity enhancement of quaternized poly(arylene ether ketone) membranes by ion segregation for vanadium redox flow batteries[J]. Science China Chemistry, 2019, 62(4): 479-490.
22	HU L, GAO L, ZHANG C K, et al. "Fishnet-like" ion-selective nanochannels in advanced membranes for flow batteries[J]. Journal of Materials Chemistry A, 2019, 7(37): 21112-21119.
23	HU L, GAO L, YAN X M, et al. Proton delivery through a dynamic 3D H-bond network constructed from dense hydroxyls for advanced ion-selective membranes[J]. Journal of Materials Chemistry A, 2019, 7(25): 15137-15144.
24	HU L, DU Y, GAO L, et al. Nanoscale solid superacid-coupled polybenzimidazole membrane with high ion selectivity for flow batteries[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(44): 16493-16502.
25	CHEN D J, QI H N, SUN T T, et al. Polybenzimidazole membrane with dual proton transport channels for vanadium flow battery applications[J]. Journal of Membrane Science, 2019, 586: 202-210.
26	XI J Y, LI Z H, YU L H, et al. Effect of degree of sulfonation and casting solvent on sulfonated poly(ether ether ketone) membrane for vanadium redox flow battery[J]. Journal of Power Sources, 2015, 285: 195-204.
27	CHU F Q, CHU X F, LÜ T, et al. Amphoteric membranes based on sulfonated polyether ether ketone and imidazolium-functionalized polyphenylene oxide for vanadium redox flow battery applications[J]. ChemElectroChem, 2019, 6(19): 5041-5050.
28	PAN J, CHEN C, LI Y, et al. Constructing ionic highway in alkaline polymer electrolytes[J]. Energy & Environmental Science, 2014, 7(1): 354-360.
29	GAO L, WANG Y, CUI C Y, et al. Anion exchange membranes with "rigid-side-chain" symmetric piperazinium structures for fuel cell exceeding 1.2 W·cm^-2 at 60 ℃[J]. Journal of Power Sources, 2019, 438: 227021.

膜	厚度/μm	离子交换容量 /mmol·g^-1	溶胀率/%	吸水率/%	离子电导率/mS·cm^-1	Fe²⁺ 渗透率×10⁹ /cm²·s^-1	Cr³⁺渗透率×10⁹ /cm²·s^-1
SPEEK	50	2.05	8.3	21.5	104	7.03	8.13
SPEEK/PEI 1%	51	1.98	7.8	19.7	99	7.28	8.25
SPEEK/PEI 3%	52	1.88	7.1	17.7	94	7.58	8.70
SPEEK/PEI 5%	50	1.64	7.1	16.3	72	6.92	7.83
SPEEK/PEI 10%	51	1.43	5.6	13.3	47	5.47	6.62

[1]	房茂霖, 张英, 乔琳, 刘淑敏, 曹中琦, 张华民, 马相坤. 铁铬液流电池技术的研究进展[J]. 储能科学与技术, 2022, 11(5): 1358-1367.
[2]	胡冶州, 王双, 申涛, 朱叶, 王得丽. 限域型贵金属氧还原反应电催化剂研究进展[J]. 储能科学与技术, 2022, 11(4): 1264-1277.
[3]	翁素婷, 刘泽鹏, 杨高靖, 张思蒙, 张啸, 方遒, 李叶晶, 王兆翔, 王雪锋, 陈立泉. 冷冻电镜表征锂电池中的辐照敏感材料[J]. 储能科学与技术, 2022, 11(3): 760-780.
[4]	李鹏辉, 吴彩文, 任建鹏, 吴文娟. 木质素作为锂离子电池电极材料的研究进展[J]. 储能科学与技术, 2022, 11(1): 66-77.
[5]	杨家豪, 施兆平, 王意波, 葛君杰, 刘长鹏, 邢巍. 用于酸性析氧反应研究的原位表征技术[J]. 储能科学与技术, 2021, 10(6): 1877-1890.
[6]	李志浩, 彭浩, 陈亚琴. 质子交换膜燃料电池膜电极组件温度分布的神经网络预测模型[J]. 储能科学与技术, 2021, 10(6): 2053-2059.
[7]	陈曦, 贺凌轩, 刘芹孝, 方叶, 龙施淳, 万忠民. 动态工况下车用燃料电池系统热力学分析[J]. 储能科学与技术, 2021, 10(4): 1416-1422.
[8]	郭德超, 郭义敏, 张啟文, 慈祥云, 何凤荣. 锂离子电池用无溶剂干法电极的制备及其性能研究[J]. 储能科学与技术, 2021, 10(4): 1311-1316.
[9]	张敬, 卢雁, 李圣, 谢光彩, 万忠民. 基于模糊PID控制的家用燃料电池热电联供系统建模与仿真[J]. 储能科学与技术, 2021, 10(3): 1117-1126.
[10]	马德正, 李培超, 张恒运. 锂离子电池隔膜在压缩过程中的流固耦合效应[J]. 储能科学与技术, 2021, 10(2): 483-490.
[11]	史佳倚, 姚莹梅, 闫佳琪, 孙超钦, 黄锋林. 磁控溅射制备的陶瓷涂层SiO₂/PP/AlF₃隔膜对电池性能影响[J]. 储能科学与技术, 2021, 10(1): 229-236.
[12]	闫晓清, 胡志宇, 刘凤泉, 李林, 谷传明, 戴熙瀛, 肖雨, 邢照亮, 周建军. 锂离子电池内隔膜褶皱的原因及消除[J]. 储能科学与技术, 2021, 10(1): 156-162.
[13]	林乙龙, 肖敏, 韩东梅, 王拴紧, 孟跃中. 锂离子电池化成技术研究进展[J]. 储能科学与技术, 2021, 10(1): 50-58.
[14]	翟俊香, 何广利, 许壮, 刘聪敏. 空冷型质子交换膜燃料电池系统效率的实验研究[J]. 储能科学与技术, 2020, 9(6): 1885-1889.
[15]	卢天骄, 黄志梅, 谢美兰, 沈越. AgF预处理稳定化锂负极及其在锂氧气电池中的应用[J]. 储能科学与技术, 2020, 9(3): 807-812.

磺化聚醚醚酮基两性离子交换膜制备及在铁-铬液流电池中的应用

Preparation of sulfonated poly（ether ether ketone） amphoteric ion exchange membrane and its application in iron-chromium redox flow battery

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 29

相关文章 15

编辑推荐

Metrics

本文评价