Chemically stable piperidinium cations for anion exchange membranes

The chemical stability of the anion exchange membranes (AEMs) is determinative towards the engineering applications of anion exchange membrane fuel cells (AEMFCs) and other AEM-based electrochemical devices, yet remains a challenge due to deficiencies in the structural design of cations. In this work, an effective design strategy for ultra-stable piperidinium cations is presented based on the systematic investigation of the chemical stability of piperidinium in harsh alkaline media. Firstly, benzyl-substituted piperidinium was degraded by about 23% in a 7 M KOH solution at 100 °C after 1436 h, which was much more stable than pyrrolidinium due to its lower ring strain. The introduction of substituent effects at the α-C position was proved to be an effective strategy for enhancing the chemical stability of the piperidinium functional group. As a result, the butyl-substituted piperidinium cation showed no obvious structural changes after being treated in the 7 M KOH solution at 100 °C for 1050 h. Afterwards, GC-MS and NMR analysis indicated that the α-C atoms in the substituents of piperidinium are fragile to the nucleophilic attack of OH^-. Based on the above results, the electronic and steric effects of different alkyl substitutions were analyzed. This work provides critical insights into the structural design of chemically stable piperidinium functional groups for the AEM and boosts its application in electrochemical devices, such as fuel cells and alkaline water electrolysis.