Exploring Novel Approaches for Enhancing the Electrochemical Performance of Li-rich Antiperovskite Cathodes for Li-ion Batteries

Current commercial intercalation cathodes are approaching their theoretical capacity edges, which limits further improvement of the energy density in Li-ion batteries. To overcome this limitation, Li-rich antiperovskite cathodes were developed, utilizing both cationic and anionic redox activities. This class of materials has the general formula (Li2TM)ChO, where TM and Ch represent a transition metal (Fe, Mn, Co) and chalcogen ion (S, Se), respectively. This work focuses on understanding the reaction mechanism, exploring novel approaches for optimizing the electrochemical performance, and developing a scalable synthesis method for the antiperovskite cathodes. Firstly, the effect of substituting S by Se in the solid-state synthesized (Li2Fe)SO on the structural and electrochemical performance is thoroughly investigated. The anionic substitution was found to improve the structural and thermal stabilities of (Li2Fe)SO material. The cyclic voltammetry data confirmed both the cationic (Fe) and anionic (S/Se) redox activities, with possibility of controlling the anionic redox potential through the anionic substitution. It was observed that the electrochemical performance exhibits a non-linear dependence on the degree of anionic substitution. Among the prepared (Li2Fe)S1-xSexO (x = 0.1-0.9) compositions, (Li2Fe)S0.7Se0.3O exhibited the best electrochemical performance with a specific capacity 245 mAhg-1 and good cycling stability at low current rate. Ex-situ and in-situ measurements suggested an enhanced structural stability of (Li2Fe)S0.7Se0.3O during electrochemical cycling compared to (Li2Fe)SO, which could be one of the reasons for its superior performance at low current rates. The second part of this work focuses on understanding the reaction mechanism of (Li2Fe)SeO prepared by solid-state reaction (SSR) method and exploring the impact of cationic substitution of Fe by Mn on its structural and electrochemical properties. Electrochemical investigations showed that the