Guo Maolian, Ban Tao, Wang Yajie, Wang Xinxin, Zhu Xiuling
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.
J Colloid Interface Sci. 2023 May 15;638:349-362. doi: 10.1016/j.jcis.2023.01.137. Epub 2023 Feb 1.
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".
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。