液流电池用含氟磺化聚芳醚酮质子交换膜的制备
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摘要
质子交换膜是液流电池的核心部件之一。以6F-双酚A(6F-BPA)、二氟二苯甲酮(DFBP)及磺化二氟二苯甲酮(SDFBP)为共聚单体,经由逐步缩聚反应,通过调整DFBP与SDFBP的投料比,合成了3种含氟磺化聚芳醚酮,采用溶液浇铸成膜的方法制备成质子交换膜。傅立叶红外、核磁氢谱及离子交换容量的表征结果表明所合成聚合物的结构与目标产物的结构相一致。当SDFBP与DFBP的投料比为1∶1时,所制备的质子交换膜具有最高的H~+传导选择性,所组装的钒流电池在充放电流为50mA/cm~2时,电池的库仑效率、电压效率、能量效率分别达到95%,78%,74%,优于同等条件下Nafion 117膜的性能。
Proton exchange membrane is a key part of vanadium redox flow battery(VRFB).Three type of fluorine-containing sulfonated poly(fluorenyl ether ketone)s(SPEEK-6Fs)with different ion exchange capacity(IEC)were synthesized from sulfonated-4,4′-difluorobenzophenone(SDFBP),4,4′-difluorobenzophenone(DFBP)and hexafluoro bisphenol A(6FBPA)by changing the molar ratio of the SDFBP and DFBP.The SPEEK-6Fs were fabricated into membranes by solution cast using DMSO as solvent.The structure of the synthesized SPEEK-6Fwas verified by characterization of FT-IR,NMR and ion exchange content.The results show that the structure of the synthesized SPEEK-6Fwas as same as the desired product's.The prepared membrane has best H+selectivity when the molar ratio of the monomer SDFBP and DFBP is 1∶1.The membrane made from SPEEK-6F50 has better comprehensive performance of single VRFB than Nafion117 with 95%of coulombic efficiency,78% of voltage efficiency and 74% of energy efficiency,when the charge-discharge current is 50mA/cm~2.
Proton exchange membrane is a key part of vanadium redox flow battery(VRFB).Three type of fluorine-containing sulfonated poly(fluorenyl ether ketone)s(SPEEK-6Fs)with different ion exchange capacity(IEC)were synthesized from sulfonated-4,4′-difluorobenzophenone(SDFBP),4,4′-difluorobenzophenone(DFBP)and hexafluoro bisphenol A(6FBPA)by changing the molar ratio of the SDFBP and DFBP.The SPEEK-6Fs were fabricated into membranes by solution cast using DMSO as solvent.The structure of the synthesized SPEEK-6Fwas verified by characterization of FT-IR,NMR and ion exchange content.The results show that the structure of the synthesized SPEEK-6Fwas as same as the desired product's.The prepared membrane has best H+selectivity when the molar ratio of the monomer SDFBP and DFBP is 1∶1.The membrane made from SPEEK-6F50 has better comprehensive performance of single VRFB than Nafion117 with 95%of coulombic efficiency,78% of voltage efficiency and 74% of energy efficiency,when the charge-discharge current is 50mA/cm~2.
引文
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[16]Yi Bibo,Dai Wenjing,Wang Lei,et al.High sulfonated poly(aryl ether ketone)membrane for vanadium flow batteries[C].The National Energy Storage Science and Technology Conference,2014.尹碧波,代文静,王雷,等.高支化磺化聚芳醚酮膜在全钒液流电池的应用[C].全国储能科学与技术大会,2014.
[17]Zhang You,Yu Junbo,Pan Jianxin,et al.The effect of vanadium ion concentration for the vanadium flow batteries polarization distribution[J].Jounal of Chemical Engineering of Chinese University,2015,29(4):920-931.张友,俞俊博,潘建欣,等.钒离子浓度对全钒液流电池极化分布的影响[J].高校化学工程学报,2015,29(4):920-931.
[18]Yan Xiaobo,Zhang Xulue,Yuan Zufeng,et al.Preparation and properties of containing fluoride poly(aromatic ether)with sulfonated side chain as proton exchange membrane[J].Journal of Polymers,2016(5).严小波,张虚略,袁祖凤,等.侧链磺化型含氟聚芳醚质子交换膜的制备及性能[J].高分子学报,2016(5).
[19]Li Zhiliang.Preparation and properties study of sulfonated poly(aryl ether ketone)materials as proton exchange membrane fuel cell[D].Changchun:Jilin University,2010.李智亮.用于质子交换膜燃料电池的磺化聚芳醚酮材料的制备与性能研究[D].长春:吉林大学,2010.
[2]Bo Jiang,Lantao Wu,Lihong Yu,et al.A comparative study of Nafion series membranes for vanadium redox flow batteries[J].Journal of Membrane Science,2016,510:18-26.
[3]Jan grosse Austing,Carolina Nunes Kirchner,Lidiya Komsiyska,et al.Layer-by-layer modification of Nafion membranes for increased life-time and efficiency of vanadium/air redox flow batteries[J].Journal of Membrane Science,2016,510:259-269.
[4]Jung H Y,Jeong S,Kwon Y.The effects of different thick sulfonated poly(ether ether ketone)membranes on performance of vanadium redox flow battery[J].Journal of the Electrochemical Society,2016,163(1):5090-5096.
[5]Wang Longfei,Ran Dongqin,Zhang Tong,et al.Preparation of b-sulfonated poly(aryl ether sulfone)cation exchange membrane and research of the electricity generating performance in MFC[J].Journal of Polymers,2014(5):657-663.王飞龙,冉冬琴,张彤,等.嵌段磺化聚芳醚砜阳离子交换膜的制备及在MFC中的发电性能研究[J].高分子学报,2014(5):657-663.
[6]Han Dongmei,Shu Dong,Wang Shuanjin,et al.The synthesis and characterization of a new type of fluoride containing fluorene poly(aryl ether ketone)of proton exchange membrane[J].Membrane Science and Technology,2010,30(1):54-59.韩东梅,舒东,王拴紧,等.一种新型含氟含芴聚芳醚酮质子交换膜的合成和表征[J].膜科学与技术,2010,30(1):54-59.
[7]Yin B,Yu L,Jiang B,et al.Nano oxides incorporated sulfonated poly(ether ether ketone)membranes with improved selectivity and stability for vanadium redox flow battery[J].Journal of Solid State Electrochemistry,2016,20(5):1271-1283.
[8]Ding F C,Wang S J,Xiao M,et al.Cross-linked sulfonated poly(phathalazinone ether ketone)s for PEM fuel cell application as proton-exchange membrane[J].Journal of Power Sources,2007,164(2):488-495.
[9]Chen Qingsong,Chen Juan,Huang Xuehong,et al.Preparation and properties study of containing fluorine sulfonated poly(aryl ether ketone)as proton exchange membrane.Jounal of Chemical Engineering of Chinese University,2013(2):277-282.陈清松,陈娟,黄雪红,等.含氟磺化聚芳醚酮质子交换膜的制备与性能研究[J].高校化学工程学报,2013(2):277-282.
[10]Wang Lei,Zhu Guangming,Wang Shuanjin,et al.Synthesis and performance study of containing part of the fluoride sulfonated poly(aryl ether)as Proton exchange membrane[J].New Chemical Materials,2007,35(5):1403-1406.王雷,朱光明,王拴紧,等.质子交换膜用部分含氟磺化聚芳醚的合成与性能研究[J].化工新型材料,2007,35(5):1403-1406.
[11]Guo Wancai.Preparation and performance study of containing the branched structure of sulfonated poly(aryl ether ketone)as proton exchange membrane[D].Changchun:Jilin University,2013.郭万才.含支化结构磺化聚芳醚酮质子交换膜的制备及性能研究[D].长春:吉林大学,2013.
[12]Li Ye,Wang Xitao,Jie Min,et al.Preparation and characterization of the linear and branched sulfonated poly(aryl ether ketone)as proton exchange membrane[C].The Doctoral Student Academic Convention,2012.李野,王喜涛,解敏,等.线性和支化磺化聚芳醚酮质子交换膜的制备与表征[C].全国博士生学术年会,2012.
[13]Yan Shijing.Preparation and performance of light sensitivity of sulfonated poly(aryl ether ketone asproton exchange membrane[D].Wuhan:South Central University for Nationalities,2011.严石静.光敏性磺化聚芳醚酮质子交换膜的制备与性能[D].武汉:中南民族大学,2011.
[14]Chen D,Wang S,Xiao M,et al.Preparation and properties of sulfonated poly(fluorenyl ether ketone)membrane for vanadium redox flow battery application[J].Journal of Power Sources 2010,195(7):2089-2095.
[15]Xu Jingmei,Zhao Ying,Cheng Longhai,et al.Preparation and properties study of containing amino crosslinked membrane sulfonated poly(aryl ether ketone sulfone)as proton exchange membrane fuel cell[J].Journal of Polymer,2013(11):1438-1444.徐晶美,赵莹,程海龙,等.质子交换膜燃料电池用含氨基磺化聚芳醚酮砜交联膜的制备与性能研究[J].高分子学报,2013(11):1438-1444.
[16]Yi Bibo,Dai Wenjing,Wang Lei,et al.High sulfonated poly(aryl ether ketone)membrane for vanadium flow batteries[C].The National Energy Storage Science and Technology Conference,2014.尹碧波,代文静,王雷,等.高支化磺化聚芳醚酮膜在全钒液流电池的应用[C].全国储能科学与技术大会,2014.
[17]Zhang You,Yu Junbo,Pan Jianxin,et al.The effect of vanadium ion concentration for the vanadium flow batteries polarization distribution[J].Jounal of Chemical Engineering of Chinese University,2015,29(4):920-931.张友,俞俊博,潘建欣,等.钒离子浓度对全钒液流电池极化分布的影响[J].高校化学工程学报,2015,29(4):920-931.
[18]Yan Xiaobo,Zhang Xulue,Yuan Zufeng,et al.Preparation and properties of containing fluoride poly(aromatic ether)with sulfonated side chain as proton exchange membrane[J].Journal of Polymers,2016(5).严小波,张虚略,袁祖凤,等.侧链磺化型含氟聚芳醚质子交换膜的制备及性能[J].高分子学报,2016(5).
[19]Li Zhiliang.Preparation and properties study of sulfonated poly(aryl ether ketone)materials as proton exchange membrane fuel cell[D].Changchun:Jilin University,2010.李智亮.用于质子交换膜燃料电池的磺化聚芳醚酮材料的制备与性能研究[D].长春:吉林大学,2010.