Practical Application of Li-Rich Materials in Halide All-Solid-State Batteries and Interfacial Reactions between Cathodes and Electrolytes

Benefiting from the advanced solid-state electrolytes (SSEs), conventional cathodes have been widely applied in all-solid-state lithium batteries (ASSLBs). However, Li-rich Mn-based (LRM) cathodes, which possess enhanced discharge capacities beyond 250 mA h g^–1, have not yet been studied in ASSLBs. In this work, the practical application of LRM cathodes in ASSLBs using a high-voltage-stability halide SSE (Li₃InCl₆, LIC) is reported for the first time. Furthermore, we decipher that the active oxygen released from LRM cathodes at a high operation voltage seriously oxidizes the LIC electrolytes, thus resulting in the large interfacial resistance between cathodes and electrolytes and hindering their industrialized application in ASSLBs. Therefore, surface chemistry engineering of LRM cathodes with an ionic conductive coating material of LiNbO₃ (LNO) is employed to stabilize the LRM/LIC interface. Consequently, the LRM-based ASSLBs deliver a high specific capacity of 221 mA h g^–1 at 0.1 C and a decent cycle life of 100 cycles. This contribution gives insights into studying the interfacial issues between LRM cathodes and halide electrolytes and sheds light on the application of LRM cathode materials in ASSLBs.