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具有增强性能和耐久性的“硫醇-烯”交联聚苯并咪唑阴离子交换膜。

"Thiol-ene" crosslinked polybenzimidazoles anion exchange membrane with enhanced performance and durability.

作者信息

Guo Maolian, Ban Tao, Wang Yajie, Wang Xinxin, Zhu Xiuling

机构信息

State Key Lab of Fine Chemicals, Department of Polymer Science & Materials, Dalian University of Technology, Dalian 116024, China.

State Key Lab of Fine Chemicals, Department of Polymer Science & Materials, Dalian University of Technology, Dalian 116024, China.

出版信息

J Colloid Interface Sci. 2023 May 15;638:349-362. doi: 10.1016/j.jcis.2023.01.137. Epub 2023 Feb 1.

Abstract

To address the "trade-off" between conductivity and stability of anion exchange membranes (AEMs), we developed a series of crosslinked AEMs by using polybenzimidazole with norbornene (cPBI-Nb) as backbone and the crosslinked structure was fabricated by adopting click chemical between thiol and vinyl-group. Meanwhile, the hydrophilic properties of the dithiol cross-linker were regulated to explore the effect for micro-phase separation morphology and hydroxide ion conductivity. As result, the AEMs with hydrophilic crosslinked structure (PcPBI-Nb-C2) not only had apparent micro-phase separation morphology and high OH conductivity of 105.54 mS/cm at 80 °C, but also exhibited improved mechanical properties, dimensional stability (swelling ratio < 15%) and chemical stability (90.22 % mass maintaining in Fenton's reagent at 80 °C for 24 h, 78.30 % conductivity keeping in 2 M NaOH at 80 °C for 2016 h). In addition, the anion exchange membranes water electrolysis (AEMWEs) using PcPBI-Nb-C2 as AEMs achieved the current density of 368 mA/cm at 2.1 V and the durability over 500 min operated at 150 mA/cm under 60 °C. Therefore, this work paves the way for constructing AEMs by introduction of norbornene into polybenzimidazole and formation of hydrophilic crosslinked structure based on "thiol-ene".

摘要

为了解决阴离子交换膜(AEMs)电导率与稳定性之间的“权衡”问题,我们以含降冰片烯的聚苯并咪唑(cPBI-Nb)为主链,通过硫醇与乙烯基之间的点击化学构建交联结构,制备了一系列交联AEMs。同时,调节二硫醇交联剂的亲水性,以探究其对微相分离形态和氢氧根离子电导率的影响。结果表明,具有亲水性交联结构的AEMs(PcPBI-Nb-C2)不仅具有明显的微相分离形态,在80℃时OH电导率高达105.54 mS/cm,而且机械性能、尺寸稳定性(溶胀率<15%)和化学稳定性均有所提高(在80℃的芬顿试剂中24小时质量保留率为90.22%,在80℃的2 M NaOH中2016小时电导率保留率为78.30%)。此外,以PcPBI-Nb-C2作为AEMs的阴离子交换膜水电解槽(AEMWEs)在2.1 V时实现了368 mA/cm²的电流密度,在60℃下150 mA/cm²运行时耐久性超过500分钟。因此,这项工作为通过将降冰片烯引入聚苯并咪唑并基于“硫醇-烯”形成亲水性交联结构来构建AEMs铺平了道路。

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