As a high‐energy‐density cathode for Li‐ion batteries, high‐Ni layered oxides, especially with ultrahigh Ni‐content, suffer from short lifespans, due in part to their unstable electrode–electrolyte interphase (EEI). Herein, the cycle life of LiNi_0.94Co_0.06O₂ is greatly extended by manipulating the EEI with a lithium bis(oxalate) (LiBOB) additive even when operated at a moderately high voltage (4.4 V vs Li/Li⁺). Impressively, the capacity retention can be increased from 61 to 80% after 500 cycles in a full cell paired with a graphite anode. Additionally, the presence of LiBOB enables a robust boron‐ and oxygen‐enriched EEI that effectively inhibits continual electrolyte decomposition and offers a stable cathode surface. Moreover, the layered architecture of the cathode–electrolyte interphase (CEI) and the anode–electrolyte interphase (AEI) at the nanometer scale is revealed by time‐of‐flight secondary ion mass spectrometry. It is demonstrated that the cathode surface chemistry can significantly influence the AEI both chemically and physically, and AEI is modified from a thick “three‐layer” to a thin “two‐layer” architecture by tuning the cathode surface chemistry with LiBOB. This work presents a correlation between the EEI characteristics and battery performance and highlights the significance of manipulating surface chemistry in developing stable high‐energy‐density Li‐ion batteries.

中文翻译：

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通过调整电解质-电解质间的相，延长高镍层状氧化物的使用寿命

作为锂离子电池的高能量密度阴极，高镍层状氧化物（特别是镍含量超高的氧化物）的使用寿命短，部分原因是电极-电解质间相（EEI）不稳定。在此，即使在中等高电压下（4.4 V vs Li / Li ⁺）操作，通过用双（草酸）锂（LiBOB）添加剂操纵EEI，也可以大大延长LiNi _0.94 Co _0.06 O ₂的循环寿命。）。令人印象深刻的是，在与石墨阳极配对的完整电池中，经过500次循环后，容量保持率可以从61％提高到80％。另外，LiBOB的存在使硼和氧富集的EEI稳定，可有效抑制电解质的连续分解并提供稳定的阴极表面。此外，通过飞行时间二次离子质谱分析揭示了纳米级阴极－电解质中间相（CEI）和阳极－电解质中间相（AEI）的分层结构。事实证明，阴极表面化学性质可以在化学和物理上显着影响AEI，并且可以通过使用LiBOB调整阴极表面化学性质，将AEI从厚的“三层”结构修改为薄的“两层”结构。