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DOE OSTI · 2476596

Amorphous Oxyhalide Matters for Achieving Lithium Superionic Conduction

Zhang, Shumin·Zhao, Feipeng·Chang, Lo-Yueh·Chuang, Yu-Chun·Zhang, Zhen·Zhu, Yuanmin·Hao, Xiaoge·Fu, Jiamin·Chen, Jiatang·Luo, Jing·Li, Minsi·Gao, Yingjie·Huang, Yining·Sham, Tsun-Kong·Gu, M. Danny·Zhang, Yuanpeng·King, Graham·Sun, Xueliang
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Abstract

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 Li 3 ZrCl 4 O 1.5 . 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. In conclusion, these findings provide deep insights into the rational design of desirable halide SEs for high-performance ASSBs.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYHalogensHeat transferInorganic compoundsIonic conductivityThermodynamic modeling

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Zhang, Shumin, Zhao, Feipeng, Chang, Lo-Yueh, Chuang, Yu-Chun, Zhang, Zhen, Zhu, Yuanmin, Hao, Xiaoge, Fu, Jiamin, Chen, Jiatang, Luo, Jing, Li, Minsi, Gao, Yingjie, Huang, Yining, Sham, Tsun-Kong, Gu, M. Danny, Zhang, Yuanpeng, King, Graham, Sun, Xueliang. 2024-01-29. Amorphous Oxyhalide Matters for Achieving Lithium Superionic Conduction. https://doi.org/10.1021/jacs.3c07343

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