Atomic-Scale Cryo-TEM Studies of the Thermal Runaway Mechanism of Li1.3Al0.3Ti1.7P3O12 Solid Electrolyte

作者：Jitong Yan, Dingding Zhu, Hongjun Ye, Haiming Sun, Xuedong Zhang, Jingming Yao, Jingzhao Chen, Lin Geng, Yong Su, Pan Zhang, Qiushi Dai, Zaifa Wang, Jing Wang, Jun Zhao, Zhaoyu Rong, Hui Li, Baiyu Guo, Satoshi Ichikawa, Dawei Gao, Liqiang Zhang, Jianyu Huang, Yongfu Tang · 发表于：ACS Energy Letters · 年份：2022 · DOI：10.1021/acsenergylett.2c01981 · 被引用次数：38 · 研究领域：Advancements in Battery Materials、Advanced Battery Materials and Technologies、Advanced Battery Technologies Research

Understanding the thermal runaway mechanism of solid-state electrolytes is critical for the development of all-solid-state Li-metal batteries (ASLMBs). Herein we employ multiscale methods including in situ optical microscopy and cryo-transmission electron microscopy combining with density functional theory to reveal the failure mechanism of Li 1.3 Al 0.3 Ti 1.7 P 3 O 12 (LATP). Li reacts with LATP to form an amorphous phase at elevated temperatures, which then crystallizes into Li 3 PO 4 and LiP with additional Li 3 P and Li 0.5 TiO 2 at even higher temperatures. The instability of the corner-sharing PO 4 tetrahedra and TiO 6 octahedra against Li at high temperature is the root cause of thermal runaway for LATP. Li diffusion into LATP causes the collapse of the PO 4 tetrahedra and TiO 6 octahedra, forming Li–O, Li–P–O, and Li–Ti–O species which release a large amount of heat, triggering thermal runaway of LATP. This work provides atomic-scale understanding of the thermal runaway of LATP, which offers an important clue to mitigate failure of ASLMBs.