Fast Bulky Anion Conduction Enabled by Free Shuttling Phosphonium Cations

Highly conductive anion-exchange membranes (AEMs) are desirable for applications in various energy storage and conversion technologies. However, conventional AEMs with bulky HCO₃ ^- or Br^- as counterion generally exhibit low conductivity because the covalent bonding restrains the tethered cationic group's mobility and rotation. Here, we report an alternative polyrotaxane AEM with nontethered and free-shuttling phosphonium cation. As proved by temperature-dependent NMR, solid-state NMR, and molecular dynamics simulation, the phosphonium cation possesses a thermally trigged shuttling behavior, broader extension range, and greater mobility, thus accelerating the diffusion conduction of bulky anions. Owing to this striking feature, high HCO₃ ^- conductivity of 105 mS cm^-1 at 90°C was obtained at a relatively lower ion-exchange capacity of 1.17 mmol g^-1. This study provides a new concept for developing highly conductive anion-exchange membranes and will catalyze the exploration of new applications for polyrotaxanes in ion conduction processes.