Interface Construction via Scavenging Oxygen Species Enables High‐Performance Li‐Rich Layered Oxide Cathode

ABSTRACT Lithium‐rich layered oxide (LRLO) is a promising material for high‐energy‐density lithium‐ion batteries (LIBs), yet its practical application is hindered by the nucleophilic attack of reactive oxygen species (ROS) on carbonate electrolytes, inducing severe interfacial incompatibility. Herein, a LiPF ₆ ‐based carbonate electrolyte modified by dual B/P‐containing additives with oxygen scavenging capability is developed to mitigate these issues. The designed electrolyte enables efficient ROS scavenging and in situ formation of a robust cathode/electrolyte interface (CEI) on the LRLO surface. The designed electrolyte not only enhances the reversibility of anionic redox reactions (ARRs) but also suppresses electrolyte decomposition and transition metal dissolution. Electrochemical tests demonstrate that the Li//LRLO cell with a high mass loading of 15 mg cm ⁻² retains 94.4% of its initial capacity after 200 cycles, while the 4.5 Ah graphite//LRLO pouch cell exhibits a higher energy density of 282.5 Wh kg ⁻¹ with stable cycling over 50 cycles. This work offers a viable strategy for interface engineering of LRLO‐based cathodes, paving the way for the development of high‐performance LIBs with long‐term cyclic stability.