自交联型磺化聚醚醚酮质子交换膜的合成
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摘要
以含3,3'-二烯丙基双酚A结构单元的聚醚醚酮为基膜材料,通过自由基加成反应在取代基上引入磺酸基团,合成侧链型磺化聚醚醚酮(SPEEK)质子交换膜.用傅里叶变换红外(FTIR)光谱、核磁共振氢谱(1H NMR)、热重分析(TG)和扫描电子显微镜(SEM)等方法对SPEEK的结构进行表征.实验结果表明,巯基丙磺酸被接枝在聚醚醚酮侧基上,SPEEK膜具有明显的亲水疏水微相分离形貌,磺酸基团相互聚集形成离子通道. SPEEK膜离子交换容量为2. 12 mmol/g,钒离子渗透率为1. 54×10-6cm~2/min,低于Nafion117膜的钒离子渗透率,阻钒能力优于Nafion117膜.以SPEEK-4膜组装电池的自放电时间约为130 h,长于Nafion117膜的66 h.电池充放电循环50次,SPEEK-4膜的库仑效率、电压效率和能量效率没有明显降低,显示出良好的稳定性.
Side chain type,sulfonated poly( ether ether ketone)( SPEEK) was prepared via free radical addition reaction using PEEK containning 3,3'-diallyl bisphenol A structural unit and 3-mercaptopropanesulphonate. The structure and morphology of SPEEK membrane were characterized by Fourier transform infrared spectroscopy( FTIR),1 H NMR,TGA and SEM. The SPEEK has high hydrophilic/hydrophobic phase separation. Water uptake, mechanical property, proton conductivity, VO2+permeability and single cell performances were investigated in order to understand the relationship between morphology and property of the membranes. The vanadium ion VO2+permeability through the SPFEK-4 membrane( IEC = 2. 12 mmol/g) is1. 54×10-6 cm~2/min,which is lower than that of Nafion membrane( 6. 04×10-6 cm~2/min). Tests of SPPEK-4 in vanadium redox batteries( VRB) demonstrate a comparable Columbic efficiency( CE) and energy efficiency( EE) to that of Nafion117 at 50 m A/cm~2,and the SPPEK-4 membrane exhibits stable performance in cell over 50 charge-discharge cycles.
Side chain type,sulfonated poly( ether ether ketone)( SPEEK) was prepared via free radical addition reaction using PEEK containning 3,3'-diallyl bisphenol A structural unit and 3-mercaptopropanesulphonate. The structure and morphology of SPEEK membrane were characterized by Fourier transform infrared spectroscopy( FTIR),1 H NMR,TGA and SEM. The SPEEK has high hydrophilic/hydrophobic phase separation. Water uptake, mechanical property, proton conductivity, VO2+permeability and single cell performances were investigated in order to understand the relationship between morphology and property of the membranes. The vanadium ion VO2+permeability through the SPFEK-4 membrane( IEC = 2. 12 mmol/g) is1. 54×10-6 cm~2/min,which is lower than that of Nafion membrane( 6. 04×10-6 cm~2/min). Tests of SPPEK-4 in vanadium redox batteries( VRB) demonstrate a comparable Columbic efficiency( CE) and energy efficiency( EE) to that of Nafion117 at 50 m A/cm~2,and the SPPEK-4 membrane exhibits stable performance in cell over 50 charge-discharge cycles.
引文
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[2] Wang W.,Luo Q. T.,Li B.,Wei X. L.,Li L. Y.,Yang Z. G.,Adv. Funct. Mater,2013,23(8),970—986
[3] Noack J.,Roznyatovskaya N.,Herr T.,Fischer P.,Angew. Chem. Int. Ed.,2015,54(34),9776—9809
[4] Ulaganathan M.,Aravindan V.,Yan Q.,Madhavi S.,Kazacos M. S.,Lim T. M.,Adv. Mat. Interfaces,2016,3(1),1—22
[5] Kim K. J.,Park M. S.,Kim Y. J.,Kim J. H.,Dou S. X.,Skyllas-Kazacos M.,J. Mat. Chem. A,2015,3,16913—16933
[6] Tang A.,Bao J.,Skyllas-Kazacos M. S.,J. Power Sources,2014,248,154—162
[7] Choi B. G.,Hong J.,Park Y. C.,Jung D. H.,Hong W. H.,Hammond P. T.,Park H. S.,ACS Nano,2011,5(6),5167—5174
[8] Luo Q. T.,Zhang H. M.,Chen J.,Qian P.,Zhai Y. F.,J. Membr. Sci.,2008,311,98—103
[9] Tao Y. Y.,Zhang X. L.,Hu Z. X.,Zhang J. Q.,Geng H.,Gao Y.,Yuan Z. F.,Bi H. P.,Chen S. W.,Wang L.,Chem. J. Chinese Universities,2016,37(4),793—800(陶应勇,张虚略,胡朝霞,张晶晶,耿慧,高颖,袁祖凤,毕慧平,陈守文,王连军.高等学校化学学报,2016,37(4),793—800)
[10] Chen K. C.,Bai W. X.,Zhao Z. P.,Liu W. F.,Yang Z.,Chem. J. Chinese Universities,2015,36(4),781—787(陈康成,白文馨,赵之平,刘文芳,杨智.高等学校化学学报,2015,36(4),781—787)
[11] Zhang S. H.,Jiang Y. W.,Chen L. Y.,Jian X. G.,Acta Polymerica Sinica,2013,(8),1993—1998(张守海,姜懿文,陈丽云,蹇锡高.高分子学报,2013,(8),1993—1998)
[12] Matsumoto K.,Higashihara T.,Ueda M.,Macromolecules,2009,42(4),1161—1166
[13] Tian S.,Meng Y.,Hay A. S.,Macromolecules,2009,42(4),1153—1160
[14] Yuan Z.,Duan Y.,Zhang H.,Li X.,Zhang H.,Vankelecom I.,Energy. Environ. Sci.,2016,9,441—447
[15] Guan Z. P.,Xiao M.,Wang S. J.,Meng Y. Z.,Euro. Polym. J.,2010,46(1),81—91
[16] Dong F. L.,Li Z. F.,Wang S. W.,Xu L. J.,Yu X. J.,Int. J. Hydrogen Energy,2011,36(5),3681—3687
[17] Cui M.,Zhang Z.,Yuan T.,Yang H.,Wu L.,Bakangura E.,Xu T.,J. Membr. Sci.,2014,465,100—106
[18] Schuster M.,de Araujo C. C.,Atanasov V.,Andersen H. T.,Kreuer K. D.,Maier J.,Macromolecules,2009,42(8),3129—3137
[19] Li L.,Zang J.,Wang Y. X.,J. Membr. Sci.,2003,226,159—167
[20] Song M. F.,Lu X. W.,Li Z. F.,Liu G. H.,Yin X. Y.,Wang Y. X.,Int. J. Hydrogen Energy,2016,41(27),12069—12081
[21] Sun P.,Li Z. F.,Wang S. W.,Yin X. Y.,J. Membr. Sci.,2018,549,660—669
[22] Li Y. Y.,Zhao X. P.,Chen Z. X.,Ding Fu. C.,Huang X. H.,Acta Polymerica Sinica,2015,(7),819—826(李奕奕,赵晓萍,陈智祥,丁富传,黄雪红.高分子学报,2015,(7),819—826)
[23] Lai A. N.,Zhou K.,Zhuo Y. Z.,Zhang Q. G.,Zhu A. M.,Ye M. L.,Liu Q. L.,J. Membr. Sci.,2016,497,99—107
[24] Chen D. Y.,Wang S. N.,Xiao M.,Meng Y. Z.,Energy. Environ. Sci.,2010,3(5),622—628
[25] Sun J. W.,Shi D. Q.,Zhong H. X.,Li X. F.,Zhang H. M.,J. Power Sources,2015,294,562—568