全钒液流电池离子交换膜的研究进展

doi:10.3969/j.issn.2095-4239.2013.02.006

摘要/Abstract

摘要： 全钒氧化还原液流电池(VRB)作为一种新兴的电化学储能系统在解决可再生能源利用方面具有良好的应用前景.离子交换膜作为全钒液流电池的关键功能材料之一,应具有钒离子透过率低,电导率高,化学稳定性好等性能.本文论述了VRB的工作原理和特点,综述了近年来国内外相关的研究进展,对商品化离子膜,新型阳离子膜,新型阴离子膜,两性离子膜在VRB中的研究应用进行了对比与分析,并指出它们各自需要改进的地方;最后提出应大力开发低成本的国产全氟磺酸离子膜,为实现VRB大规模的产业化奠定基础.

关键词: 全钒氧化还原液流电池, 离子交换膜, 储能效率, 化学储能

Abstract: Ion exchange membranes are crucial to vanadium redox flow batteries (VRB). Such components should have a low permeability for vanadium ions, a high conductivity and chemical stability. This paper briefly introduces the principle and characteristics of VRB. A review is then given of the recent research and development progress in ion exchange membrane, covering commercial ion exchange membranes, cation exchange membranes, anion exchange membranes as well as amphoteric ion exchange membranes. Comparison of these membranes and recommendations for further improvements are then given. Finally, development of low cost perfluorosulfonated membranes is proposed as a key to large scale industrial take-up of the VRB technology.

Key words: vanadium redox flow battery, ion exchange membrane, energy storage efficiency, chemical energy storage

中图分类号:

TM912.9

牛洪金, 唐军柯, 张永明, 张恒. 全钒液流电池离子交换膜的研究进展[J]. 储能科学与技术, 2013, 2(2): 132-139.

NIU Hongjin, TANG Junke, ZHANG Yongming, ZHANG Heng. Review on ion exchange membranes for vanadium redox flow battery applications[J]. Energy Storage Science and Technology, 2013, 2(2): 132-139.

参考文献

[1] Zhang Huamin(张华民). Development and application status of energy storage technologies[J]. Energy Storage Science and Technology (储能科学与技术),2012,1(1):58-63.
[2] Sum E,Rychcik M,Skyllas-Kazacos M. Investigation of the V(V)/V(IV) system for use in the positive half-cell of a redox battery[J]. Journal of Power Sources ,1985,16(8):85-95.
[3] Skyllas-Kazacos M,Rychcik M,Robins R, et al . New all vanadium redox flow cell[J]. Journal of the Electrochemical Society ,1986,133(10):1057-1058.
[4] Fabjan C,Garche J,Harrer B, et al . The vanadium redox-battery:An efficient storage unit for photovoltaic systems[J]. Electrochim Acta ,2001,47(5):825-831.
[5] Zhong S,Skyllas-Kazacos M. Electrochemical behaviour of vanadium(V)/vanadium(IV) redox couple at graphite electrodes[J]. Journal of Power Sources ,1992,39(2):1-9.
[6] Mohammadi T,Chieng S,Skyllas-Kazacos M. Water transport commercial ion exchange membranes in the vanadium redox flow redox couple study across battery[J]. Journal of Membrane Science ,1997,133(2):151-159.
[7] Mohammadi T,Skyllas-Kazacos M. Modification of anion-exchange membranes for vanadium redox flow battery applications[J]. Journal of Power Sources ,1996,63(2):179-186.
[8] Menictas C,Cheng M,Skyllas-Kazacos M. Evaluation of NH 4 VO 3 derived electrolyte for vanadium redox flow battery[J]. Journal of Power Sources ,1993,45(1):43-54.
[9] Hwang G,Ohya H. Crosslinking of anion exchange membrane by accelerated electron radiation as a separator for the all-vanadium redox flow battery[J]. Journal of Membrane Science ,1997,132(1):55-61.
[10] Mohammadi T,Skyllas-Kazacos M. Characterization of novel composite membrane for redox flow battery applications[J]. Journal of Membrane Science ,1995,98(1-2):77-87.
[11] Mohammadi T,Skyllas-Kazacos M. Use of polyelectrolyte for incorporation of ion-exchange groups in composite membranes for vanadium redox flow battery applications[J]. Journal of Power Sources ,1995,56(1):91-96.
[12] Mohammadi T,Skyllas-Kazacos M. Preparation of sulfonated composite membrane for vanadium redox flow battery applications[J]. Journal of Membrane Science ,1995,107(1-2):35-45.
[13] Tian Bo,Yan Chuanwei,Wang Fuhui. Proton conducting composite membrane from daramie/nafion for vanadium redox flow battery[J]. Journal of Membrane Science ,2004,234(1-2):51-54.
[14] Luo Qingtao,Zhang Huamin,Chen Jian, et al . Preparation and characterization of Nafion/SPEEK layered composite membrane and its application in vanadium redox flow battery[J]. Journal of Membrane Science ,2008,325(2):553-558.
[15] Xi Jingyu,Wu Zenghua,Teng Xiangguo, et al . Self-assembled polyelectrolyte multilayer modified Nafion membrane with suppressed vanadium ion crossover for vanadium redox flow batteries[J]. Journal of Materials Chemistry ,2008,18(11):1232-1238.
[16] Zeng Jie,Jiang Chunping,Wang Yaohui, et al . Studies on polypyrole modified Nafion membrane for vanadium redox flow battery[J]. Electrochem. Commun. ,2008,10(3):372-375.
[17] Schwenzer B,Kim S,Vijayakumar M,et al. Correlation of structural differences between Nafion/polyaniline and Nafion/polypyrrole composite membranes and observed transport properties[J]. Journal of Membrane Science ,2011,372(1-2):11-19.
[18] Jiang R,Knuz H,Fenton J. Composite silica/Nafion ® membranes prepared by tetraethylorthosilicate sol-gel reaction and solution casting for direct methanol fuel cells[J]. Journal of Membrane Science ,2006,272(1-2):116-124.
[19] Kim H Shul Y,Han H. Sulfonic-functionalized heteropolyacid-silica nanoparticles for high temperature operation of a direct methanol fuel cell[J]. Journal of Power Sources ,2006,158(1):137-142.
[20] Xi Jingyu,Wu Zenghua,Qiu Xinping, et al . Nafion/SiO 2 hybrid membrane for vanadium redox flow battery[J]. Journal of Power Sources ,2007,166(2):531-536.
[21] Sang Shangbin,Wu Qiumei,Huang Kelong. Preparation of zirconium phosphate(ZrP)/ Nafion1135 composite membrane and H + /VO 2+ transfer property investigation[J]. Journal of Membrane Science ,2007,305(1-2):118-124.
[22] Teng Xiangguo,Zhao Yongtao,Xi Jingyu, et al . Nafion/organic silica modified TiO 2 composite membrane for vanadium redox flow battery via in situ sol-gel reactions[J]. Journal of Membrane Science ,2009,341(1-2):149-154.
[23] Vijayakumar M,Schwenzer B,Kim S, et al . Investigation of local environments in Nafion-SiO 2 composite membranes used in vanadium redox flow batteries[J]. Solid State Nuclear Magnetic Resonance ,2012,42:71-80.
[24] Luo Qingtao,Zhang Huamin,Chen Jian, et al . Modification of Nafion membrane using interfacial polymerization for vanadium redox flow battery applications[J]. Journal of Membrane Science ,2008,311(1-2):98-103.
[25] Ling Xiao,Jia Chuankun,Liu Jianguo, et al . Preparation and characterization of sulfonated poly ether sulfone)/sulfonated poly(ether ether ketone) blend membrane for vanadium redox flow battery[J]. Journal of Membrane Science ,2012,415-416:306-312.
[26] Wei Wenping,Zhang Huamin,Li Xianfeng, et al . Poly(tetrafluoroethylene) reinforced sulfonated poly(ether ether ketone) membranes for vanadium redox flow battery application[J]. Journal of Power Sources ,2012,208:421-425.
[27] Jia Chuankun,Liu Jianguo,Yan Chuanwei. A multilayered membrane for vanadium redox flow battery[J]. Journal of Power Sources ,2012,203:190-194.
[28] Wang Nanfang,Peng Sui,Wang Hongmei, et al . A SPPEK/WO 3 hybrid membrane fabricated via hydrothermal method for vanadium redox flow battery[J]. Electrochemistry Communications ,2012,17:30-33.
[29] Sang Shangbin(桑商斌),Huang Kelong(黄可龙),Shi Ruicheng(石瑞成), et al . Research on PVA-ZrP composite membrane as separator in all vanadium redox flow battery[J]. Journal of Central South University of Technolog y( natural science )(中南大学学报:自然科学版),2005,36(6):1011-1016.
[30] Wang Baoguo(王保国),Long Fei(龙飞),Fan Yongsheng(范永生), et al . A preparation method of proton conduction membrane:China(中国),200910077024.6[P]. 2009-07-08.
[31] Qingge Letu(青格乐图),Liu Ping(刘平),Fan Yongsheng(范永生), et al . Ion conductive membrane with interpenetration network(IPN)prepared by pvdf/poly(lonic liquid)s blend[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报),2011,25(3):501-506.
[32] Long Fei(龙飞),Chen Jinqing(陈金庆),Wang Baoguo(王保国). Preparation of ion exchange membrane for all vanadium flow redox battery[J]. Journal of Tianjin Polytechnic University (天津工业大学学报),2008,27(4):9-11.
[33] Qiu Jingyi,Zhao Long,Zhai Maolin, et al . Pre-irradiation of styrene and maleic anhydride onto PVDF membrane and subsequent sulfonation for application in vanadium redox batteries[J]. Journal of power sources ,2008,177:617-623.
[34] Zhang Hongzhang,Zhang Huamin,Li Xianfeng, et al . Nanofiltration (NF) membranes:the next generation separators for all vanadium redox flow batteries (VRBs)[J]. Energy & Environmental Science ,2011,4:1676-1679.
[35] Zhang Hongzhang,Zhang Huamin,Li Xianfeng, et al . Silica modified nanofiltration membranes with improved selectivity for redox flow battery application[J]. Energy Environ. Sci. ,2012,5:6299-6303.
[36] Jian Xigao,Yan Chun,Zhang Huamin, et al . Synthesis and characterization of quaternized poly(phthalazinone ether sulfone ketone) for anion-exchange membrane[J]. Chinese Chemistry Letter ,2007,18(10):1269-1272.
[37] Xing Dongbo,Zhang Shouhai,Yin Chunxiang, et al . Preparation and characterization of chloromethylated/quaternized poly(phthalazinone ether sulfone) anion exchange membrane[J]. Material Science and Engineering B ,2009,157:1-5.
[38] Xing Dongbo,Zhang Shouhai,Yin Chunxiang, et al . Effect of amination agent on the proterties of quaternized poly (phthalazinone ether sulfone) anion exchange membrane for vanadium redox flow battery application[J]. Journal of Membrane Science ,2010,354(1-2):68-73.
[39] Zhang Bengui,Zhang Shouhai,Xing Dongbo, et al . Quaternized poly(phthalazinone ether ketone ketone) anion exchange membrane with low permeability of vanadium ions for vanadium redox flow battery[J]. Application Journal of Power Sources ,2012,217:296-302.
[40] Zhang Qi,Dong Quanfeng,Zheng Mingsen, et al . The preparation of a novel anionexchange membrane and its application in all-vanadium redox batteries[J]. Journal of Membrane Science ,2012,421-422:232-237.
[41] Qiu Jingyi,Ni Jiangfeng,Zhai Maolin, et a1 . Radiation grafting of styrene and maleic anhydride onto PTFE membranes and sequent sulfonation for applications of vanadium redox battery[J]. Radiation Physics and Chemistry ,2007,12(l):1-5.
[42] Qiu Jingyi,Li Mengyuan,Ni Jiangfeng, et al . Preparation of ETFE-based anion exchange membrane to reduce permeability of vanadium ions in vanadium redox battery[J]. Journal of Membrane Science ,2007,297(1-2):174-180.
[43] Qiu Jingyi,Zhang Junzhi,Chen Jinhua, et al . Amphoteric ion exchange membrane synthesized by radiation-induced graft copolymerization of styrene and dimethylaminoethyl methacrylate into PVDF film for vanadium redox flow battery applications[J]. Journal of Membrane Science ,2009,334(1-2):9-15.
[44] Hua Guowen,Wang Yu,Ma Jun, et al . A novel amphoteric ion exchange membrane synthesized by radiation-induced grafting α -methylstyrene and N , N -dimethylaminoethyl methacrylate for vanadium redox flow battery application[J]. Journal of Membrane Science ,2012,407-408:184-192.
[45] Qiu Jingyi,Zhai Maolin,Chen Jinhua, et al . Performance of vanadium redox flow battery with a novel amphoteric ion exchange membrane synthesized by two-step grafting method[J]. Journal of Membrane Science ,2009,342(1-2):215-220.