Amorphous Oxyhalide Matters for Achieving Lithium Superionic Conduction.

作者：Shumin Zhang, Fei-Peng Zhao, L. Chang, Yu-Chun Chuang, Zhen Zhang, Yuan-Min Zhu, Xiaoge Hao, Jia-Min Fu, Jiatang Chen, Jing Luo, Min-Si Li, Yingjie Gao, Yining Huang, Tsun-Kong Sham, M. Gu, Yuanpeng Zhang, Graham King, Xue-Liang Sun · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.3c07343 · 被引用次数：155 · 研究领域：Medicine

The recently surged halide-based solid electrolytes (SEs) are great candidates for high-performance all-solid-state batteries (ASSBs), due to their decent ionic conductivity, wide electrochemical stability window, and good compatibility with high-voltage oxide cathodes. In contrast to the crystalline phases in halide SEs, amorphous components are rarely understood but play an important role in Li-ion conduction. Here, we reveal that the presence of amorphous component is common in halide-based SEs that are prepared via mechanochemical method. The fast Li-ion migration is found to be associated with the local chemistry of the amorphous proportion. Taking Zr-based halide SEs as an example, the amorphization process can be regulated by incorporating O, resulting in the formation of corner-sharing Zr-O/Cl polyhedrons. This structural configuration has been confirmed through X-ray absorption spectroscopy, pair distribution function analyses, and Reverse Monte Carlo modeling. The unique structure significantly reduces the energy barriers for Li-ion transport. As a result, an enhanced ionic conductivity of (1.35 ± 0.07) × 10-3 S cm-1 at 25 °C can be achieved for amorphous Li3ZrCl4O1.5. In addition to the improved ionic conductivity, amorphization of Zr-based halide SEs via incorporation of O leads to good mechanical deformability and promising electrochemical performance. These findings provide deep insights into the rational design of desirable halide SEs for high-performance ASSBs...