Direct Observation of Li Migration into V₅S₈: Order to Antisite Disorder Intercalation Followed by the Topotactic-Based Conversion Reaction

Two-dimensional transition-metal dichalcogenides hold great potential in rechargeable lithium-ion batteries. Their electrochemical properties are closely related to the structural evolutions during lithium-ion migration. Understanding these migration/reaction mechanisms is important to help improve battery performance. Herein, we report the real-time and atomic-scale observation of phase transitions during the lithiation and delithiation for V₅S₈ via in situ electron diffraction and high-resolution transmission electron microscopy techniques. We find that the phase transformation proceeds via a sequence of order to antisite disorder intercalation and topotactic-based conversion reaction. During the intercalation reaction, the lithium ion destroys the orderings of the interstitial V with the formation of Li/V antisite. Such a reaction is found to be reversible, i.e., the extraction of lithium from Li_xV₅S₈ leads to the recovery of V orderings. The conversion reaction involves heterogeneous nucleation of Li₂S with 3–20 nm nanodomains, which maintain the crystallographic integrity with Li_xV₅S₈. These findings elucidate the complex interactions between the lithium ion and host V₅S₈ during ionic migration in solids, which should be helpful in understanding the relationship between phase transformation kinetics and battery performance.