Origin of the Seriously Limited Anionic Redox Reaction of Li-Rich Cathodes in Sulfide All-Solid-State Batteries

Li-rich layered oxide (LLO) cathode materials with mixed cationic and anionic redox reactions display much higher specific capacity than other traditional layered oxide materials. However, the practical specific capacity of LLO during the first cycle in sulfide all-solid-state lithium-ion batteries (ASSLBs) is extremely low. Herein, the capacity contribution of each redox reaction in LLO during the first charging process is qualitatively and quantitatively analyzed by comprehensive electrochemical and structural measurements. The results demonstrate that the cationic redox of the LiTMO₂ (TM = Ni, Co, Mn) phase is almost complete, while the anionic redox of the Li₂MnO₃ phase is seriously limited due to the sluggish transport kinetics and severe LLO/Li₆PS₅Cl interface reaction at high voltage. Therefore, the poor intrinsic conductivity and interface stability during the anionic redox jointly restrict the capacity release or delithiation/lithiation degree of LLO during the first cycle in sulfide ASSLBs. This study reveals the origin of the seriously limited anionic redox reaction in LLO, providing valuable guidance for the bulk and interface design of high-energy-density ASSLBs.