一种新型聚苯并咪唑阴离子交换膜的制备与性能研究  

Synthesis and properties of a new kind of polybenzimidazole anion exchange membranes

作　　者：冯美佳 刘功益 张崇印 郭晓霞[1] 房建华[1] Feng Meijia;Liu Gongyi;Zhang Chongyin;Guo Xiaoxia;Fang Jianhua(School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240;Shanghai Aerospace Equipment Manufacturer Co.,Ltd.,Shanghai Engineering Research Center of Specialized Polymer Materials for Aerospace,Shanghai 200245)

机构地区：[1]上海交通大学化学化工学院,上海200240 [2]上海航天设备制造总厂有限公司,上海航天特种环境高分子功能材料工程技术研究中心,上海200245

出　　处：《化工新型材料》2022年第12期109-116,共8页New Chemical Materials

基　　金：国家“973”计划项目(2014CB643600)。

摘　　要：通过两步反应合成一种新型双环氧端基季铵盐TQ,以该季铵盐为交联剂,利用其结构中的环氧基与一种聚苯并咪唑(H_(2)N-PBI)的侧氨基反应,通过控制环氧基与氨基的摩尔比,制备了一系列具有不同离子交换容量的新型聚苯并咪唑阴离子交换膜H_(2)N-PBI-TQ(x/y)(x/y指聚合物H_(2)N-PBI的侧氨基与季铵盐TQ的环氧基团摩尔比)。以双酚A二缩水甘油醚为共交联剂,通过控制这两种交联剂的摩尔比,制备了一系列具有不同交联密度的新型聚苯并咪唑阴离子交换膜H_(2)N-PBI-TQ(x)-A。结果表明:这些阴离子交换膜具有良好的力学性能和热稳定性,且随着离子交换容量的升高,膜的吸水率、溶胀率及离子电导率也相应升高。与由Nafion212膜组装的钒液流单电池相比,由H_(2)N-PBI-TQ(1∶1.0)-A组装的单电池在电流密度80mA/cm^(2)下,有更大的充放电容量以及更高的能量效率,并且在该单电池充放电循环100圈之后,库仑效率、电压效率以及能量效率均未出现明显的下降,同时还保持了比较高的放电残余容量(57%),显示出良好的循环稳定性。A new kind of diepoxy-terminated quaternary ammonium salt(TQ) was synthesized via two-step reactions.The TQ was used as a crosslinking agent, and the cross-linking occurred between the epoxy groups of TQ and the pendant amino group of a polybenzimidazole(H_(2)N-PBI).By controlling the molar ratio of the epoxy group to the amino group, a series of new polybenzimidazole anion exchange membranes H_(2)N-PBI-TQ(x/y) with different ion exchange capacities were prepared.Bisphenol A diglycidyl ether was employed as a co-crosslinking agent, by controlling the molar ratio of the two crosslinking agents, a series of new polybenzimidazole anion exchange membranes H_(2)N-PBI-TQ(x)-A with different crosslinking densities were further prepared.These anion exchange membranes had good mechanical properties and thermal stability.As the increase of ion exchange capacity, the water absorption, swelling rate and ion conductivity of these membranes also increased accordingly.Compared with the vanadium flow battery assembled with Nafion212 membrane, the battery assembled with the H_(2)N-PBI-TQ(1∶1.0)-A showed higher voltage efficiency, higher energy efficiency and larger charge-discharge capacity at a high current density(80 mA/cm^(2)).Furthermore, after the battery underwent charge-discharge for 100 cycles at a high current density(80 mA·cm^(-2)),its coulombic efficiency, voltage efficiency and energy efficiency didn’t decrease significantly, and retained a high residual discharge capacity of 57%,indicating good cycle stability of the battery.

关 键 词：聚苯并咪唑 阴离子交换膜 钒液流电池 循环稳定性 

分 类 号：TM911.48[电气工程—电力电子与电力传动]