Ge Xiaolin, He Yubin, Zhang Kaiyu, Liang Xian, Wei Chengpeng, Shehzad Muhammad A, Song Wanjie, Ge Zijuan, Li Geng, Yu Weisheng, Wu Liang, Xu Tongwen
CAS Key Laboratory of Soft Matter Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials, School of Chemistry and Materials Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026, China.
School of Chemistry and Material Engineering, Huainan Normal University, Huainan, Anhui 232001, China.
Research (Wash D C). 2021 Aug 31;2021:9762709. doi: 10.34133/2021/9762709. eCollection 2021.
Highly conductive anion-exchange membranes (AEMs) are desirable for applications in various energy storage and conversion technologies. However, conventional AEMs with bulky HCO 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 HCO conductivity of 105 mS cm at 90°C was obtained at a relatively lower ion-exchange capacity of 1.17 mmol g. 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.
高导电性阴离子交换膜（AEMs）在各种能量存储和转换技术中具有重要应用价值。然而，传统的以体积较大的HCO 或Br作为抗衡离子的AEMs通常表现出低导电性，因为共价键限制了连接的阳离子基团的迁移率和旋转。在此，我们报道了一种具有非连接且自由穿梭的鏻阳离子的新型聚轮烷AEMs。通过变温核磁共振、固态核磁共振和分子动力学模拟证明，鏻阳离子具有热触发的穿梭行为、更宽的伸展范围和更大的迁移率，从而加速了体积较大阴离子的扩散传导。由于这一显著特性，在相对较低的离子交换容量1.17 mmol g下，于90°C时获得了105 mS cm的高HCO 电导率。本研究为开发高导电性阴离子交换膜提供了新的概念，并将推动聚轮烷在离子传导过程中的新应用探索。
