Li‐rich Mn‐based layered oxides (LLO) hold great promise as cathode materials for lithium‐ion batteries (LIBs) due to their unique oxygen redox (OR) chemistry, which enables additional capacity. However, the LLOs face challenges related to the instability of their OR process due to the weak transition metal (TM)‐oxygen bond, leading to oxygen loss and irreversible phase transition that results in severe capacity and voltage decay. Herein, a synergistic electronic regulation strategy of surface and interior structures to enhance oxygen stability is proposed. In the interior of the materials, the local electrons around TM and O atoms may be delocalized by surrounding Mo atoms, facilitating the formation of stronger TM─O bonds at high voltages. Besides, on the surface, the highly reactive O atoms with lone pairs of electrons are passivated by additional TM atoms, which provides a more stable TM─O framework. Hence, this strategy stabilizes the oxygen and hinders TM migration, which enhances the reversibility in structural evolution, leading to increased capacity and voltage retention. This work presents an efficient approach to enhance the performance of LLOs through surface‐to‐interior electronic structure modulation, while also contributing to a deeper understanding of their redox reaction.

中文翻译：

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调节金属氧的电子分布以增强富锂层状阴极的氧稳定性

富锂锰基层状氧化物（LLO）因其独特的氧氧化还原（OR）化学性质而有望成为锂离子电池（LIB）的正极材料，从而实现额外的容量。然而，由于过渡金属（TM）-氧键较弱，LLO面临着与其OR过程不稳定相关的挑战，导致氧损失和不可逆相变，从而导致严重的容量和电压衰减。在此，提出了一种表面和内部结构的协同电子调节策略以增强氧稳定性。在材料内部，TM和O原子周围的局域电子可能会被周围的Mo原子离域，从而促进在高电压下形成更强的TM─O键。此外，表面上具有孤对电子的高活性O原子被额外的TM原子钝化，从而提供了更稳定的TM─O骨架。因此，这种策略可以稳定氧并阻碍TM迁移，从而增强结构演化的可逆性，从而提高容量和电压保持力。这项工作提出了一种通过表面到内部电子结构调制来增强 LLO 性能的有效方法，同时也有助于更深入地了解其氧化还原反应。