Halide Superionic Conductors with Non‐Close‐Packed Anion Frameworks
Jin‐Da Luo, Yixi Zhang, Xiao-Bin Cheng, Feng Li, Hao‐Yuan Tan, Meiyu Zhou, Ziwei Wang, Xudong Hao, Yi‐Chen Yin, Bin Jiang, Hong‐Bin Yao
Abstract
Abstract Halide superionic conductors (SICs) are drawing significant research attention for their potential applications in all‐solid‐state batteries. A key challenge in developing such SICs is to explore and design halide structural frameworks that enable rapid ion movement. In this work, we show that the close‐packed anion frameworks shared by traditional halide ionic conductors face intrinsic limitations in fast ion conduction, regardless of structural regulation. Beyond the close‐packed anion frameworks, we identify that the non‐close‐packed anion frameworks have great potential to achieve superionic conductivity. Notably, we unravel that the non‐close‐packed UCl 3 ‐type framework exhibit superionic conductivity for a diverse range of carrier ions, including Li + , Na + , K + , and Ag + , which are validated through both ab initio molecular dynamics simulations and experimental measurements. We elucidate that the remarkable ionic conductivity observed in the UCl 3 ‐type framework structure stems from its significantly more distorted site and larger diffusion channel than its close‐packed counterparts. By employing the non‐close‐packed anion framework as the key feature for high‐throughput computational screening, we also identify LiGaCl 3 as a promising candidate for halide SICs. These discoveries provide crucial insights for the exploration and design of novel halide SICs.