High-capacity cobalt-free lithium-rich manganese-based oxide (LMNO) is a crucial representative of high-energy-density lithium-ion batteries (LIBs). However, the collaboration failure mechanism (CFM) between LMNO and electrolyte always leads to irreversible oxygen loss, harmful electrolyte decomposition, aggravated structural rearrangement, and severe interfacial side reactions, thereby triggering a sustained decrease in electrochemical performance. Therefore, capturing reactive oxygen species and generating the cathode-electrolyte-interface (CEI) layer shows the potential to resolve these typical issues induced by CFM propagation. Herein, an amine-functionalized mesoporous molecular sieve (NASM) additive with active oxygen/water scavenging capability was designed to construct a multifunctional self-reconstructive CEI layer with modified mechanical/electrochemical stability. Meanwhile, the additive-induced anti-fluoridation protective layer was synchronously generated to synergistically regulate the diffusion of lithium ions and electrons during the CEI reconstruction process. Benefiting from these advantages, the LMNO cathode with NASM-containing electrolyte presented outstanding cycle stability, with only ∼0.06% (1 C) and ∼0.07% (5 C) capacity attenuation per cycle during long-term cycling. This additive-induced multifunctional self-reconstructive CEI layer design provides new insights into reducing undesired CFM propagation to achieve a high-stability and high-energy-density LMNO system for advanced LIBs.

高容量无钴富锂锰基氧化物（LMNO）是高能量密度锂离子电池（LIBs）的重要代表。然而，LMNO与电解质之间的协同失效机制（CFM）总是导致不可逆的氧损失、有害的电解质分解、加剧的结构重排和严重的界面副反应，从而引发电化学性能的持续下降。因此，捕获活性氧并生成阴极电解质界面 (CEI) 层显示出解决这些由 CFM 传播引起的典型问题的潜力。在此处，设计了一种具有活性氧/水清除能力的胺功能化介孔分子筛 (NASM) 添加剂，以构建具有改进的机械/电化学稳定性的多功能自重构 CEI 层。同时，同步生成添加剂诱导的抗氟化保护层，以协同调节CEI重建过程中锂离子和电子的扩散。受益于这些优势，含有 NASM 电解质的 LMNO 正极表现出出色的循环稳定性，在长期循环过程中每个循环的容量衰减仅为 ~0.06%（1 C）和~0.07%（5 C）。