Direct Visualization of Li Dendrite Effect on LiCoO 2 Cathode by In Situ TEM

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2018-11, Vol.14 (52)
• Main Authors: Yang, Zhenzhong, Ong, Phuong-Vu, He, Yang, Wang, Le, Bowden, Mark E., Xu, Wu, Droubay, Timothy C., Wang, Chongmin, Sushko, Peter V., Du, Yingge
• Format: Article
• Language: English
• Subjects: In situ transmission electron microscopy (TEM), LiCoO2, STEM, Lithium dendrite, Phase transition
• ISSN: 1613-6810; 1613-6829
• DOI: 10.1002/smll.201803108

Li dendrites are known to cause deterious, and in many cases catastrophic, effect on the performance of Li rechargeable batteries. However, the mechanistic failure mechanism of cathodes upon in contact with Li metal is far from clear. In this study, using in situ transmission electron microscopy, we directly visualize at an atomic scale the interaction of Li dendrites with well-defined, epitaxial thin films of LiCoO2, the most widely used cathode material. We show that a spontaneous and prompt chemical reaction is trigged once the Li contact is made, leading to expansion and amorphization of the LiCoO2 structure, with Li2O and Co metal being the final reaction products. A topotactic phase transition is identified close to the reaction front, resulting in the formation of CoO as a metastable intermediate. Dynamic structural and chemical imaging in combination with ab inito simulations reveal that a high density of antiphase grain boundaries are formed at the reaction front, which are critical for enabling the short-range topotactic reactions and long-range Li propagation. The fundamental insights are of general importance in mitigating Li dendrites related issues and guiding the design principle for more robust energy materials.