Triggering O-related anionic redox reactivity can introduce additional capacity in Li-rich layered oxide (LRLO) cathode, while, activated oxygen species also threatens to electrode-electrolyte interface stability. Herein, revealed by in-situ SERS/Raman, we demonstrate that enrichment of superoxo-related species on LRLO surface would significantly aggravate electrolyte degradation by nucleophilic attack, and confuse/deteriorate the architecture of cathode electrolyte interface (CEI) on LRLO. Through rational introducing LiBOB as a boron-contained electrolyte additive, enhanced CEI was achieved with BOB-derived cross-linking and B-F/B_xO_y polymeric components. More importantly, benefitting from its synergy effect with LiPF₆, the sustained release of LiDFOB acts as a superoxo scavenger, which efficiently eliminates related nucleophilic attack. Tailoring the CEI into a uniform, dense, and stable passivate protection front-face, LiBOB additive enhances the cycling stability of LRLO, delivered 92.5% capacity retention (300 cycles). This work arouses reconsideration on the design/modification principle of electrolyte for LRLO cathode, and emphasizes the in-situ superoxo scavenging process.

触发与 O 相关的阴离子氧化还原反应可以在富锂层状氧化物 (LRLO) 正极中引入额外的容量，而活化的氧物质也会威胁到电极-电解质界面的稳定性。在此，通过原位 SERS/Raman 揭示，我们证明了 LRLO 表面上超氧相关物质的富集会显着加剧电解质通过亲核攻击而降解，并混淆/恶化 LRLO 上的阴极电解质界面 (CEI) 的结构。通过合理引入 LiBOB 作为含硼电解质添加剂，通过 BOB 衍生的交联和 BF/B _x O _y聚合物组分实现了增强的 CEI。更重要的是，得益于其与 LiPF _{6的协同效应}，LiDFOB 的持续释放作为一种超氧清除剂，有效地消除了相关的亲核攻击。LiBOB 添加剂将 CEI 定制为均匀、致密且稳定的钝化保护正面，增强了 LRLO 的循环稳定性，提供 92.5% 的容量保持率（300 次循环）。这项工作引起了对 LRLO 正极电解液设计/修改原理的重新思考，并强调了原位超氧清除过程。