Yin Liqiang, Ren Rong, He Lanlan, Zheng Wentao, Guo Yu, Wang Linqin, Lee Husileng, Du Jian, Li Zhiheng, Tang Tang, Ding Guoheng, Sun Licheng
Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science and Research Center for Industries of the Future, Westlake University, 600 Dunyu Road, Hangzhou, 310030, Zhejiang Province, China.
Angew Chem Int Ed Engl. 2024 May 6;63(19):e202400764. doi: 10.1002/anie.202400764. Epub 2024 Apr 8.
Anion exchange membranes (AEMs) are core components in anion exchange membrane water electrolyzers (AEM-WEs). However, the stability of functional quaternary ammonium cations, especially under high temperatures and harsh alkaline conditions, seriously affects their performance and durability. Herein, we synthesized a 1-methyl-3,3-diphenylquinuclidinium molecular building unit. Density functional theory (DFT) calculations and accelerated aging analysis indicated that the quinine ring structure was exceedingly stable, and the S2 degradation mechanism dominated. Through acid-catalyzed Friedel-Crafts polymerization, a series of branched poly(aryl-quinuclidinium) (PAQ-x) AEMs with controllable molecular weight and adjustable ion exchange capacity (IEC) were prepared. The stable quinine structure in PAQ-x was verified and retained in the ex situ alkaline stability. Furthermore, the branched polymer structure reduces the swelling rate and water uptake to achieve a tradeoff between dimensional stability and ionic conductivity, significantly improving the membrane's overall performance. Importantly, PAQ-5 was used in non-noble metal-based AEM-WE, achieving a high current density of 8 A cm at 2 V and excellent stability over 2446 h in a gradient constant current test. Based on the excellent alkaline stability of this diaryl-quinuclidinium group, it can be further considered as a multifunctional building unit to create multi-topological polymers for energy conversion devices used in alkaline environments.
阴离子交换膜(AEMs)是阴离子交换膜水电解槽(AEM-WEs)的核心组件。然而,功能性季铵阳离子的稳定性,尤其是在高温和苛刻的碱性条件下,严重影响其性能和耐久性。在此,我们合成了一种1-甲基-3,3-二苯基喹核铵分子构建单元。密度泛函理论(DFT)计算和加速老化分析表明,喹啉环结构极其稳定,且以S2降解机制为主导。通过酸催化的傅克聚合反应,制备了一系列分子量可控且离子交换容量(IEC)可调的支化聚(芳基喹核铵)(PAQ-x)AEMs。PAQ-x中稳定的喹啉结构得到了验证,并在非原位碱性稳定性测试中得以保留。此外,支化聚合物结构降低了溶胀率和吸水率,从而在尺寸稳定性和离子电导率之间实现了平衡,显著提高了膜的整体性能。重要的是,PAQ-5被用于非贵金属基AEM-WE中,在2 V电压下实现了8 A cm的高电流密度,并在梯度恒流测试中在2446 h内表现出优异的稳定性。基于这种二芳基喹核铵基团出色的碱性稳定性,它可进一步被视为一种多功能构建单元,用于制备适用于碱性环境能量转换装置的多拓扑聚合物。