The interfacial compatibility between sulfide solid electrolyte (SSE) and Ni-rich layered oxide (NRLO) cathode is critical for high-performance sulfide all-solid-state Li-ion batteries (SASSLIBs). However, the reasons for interfacial/capacity degradation of SASSLIBs are not yet clearly resolved. Herein, the impacts of surface structures and chemical environments of LiNi_0.83Co_0.11Mn_0.06O₂ (NCM83) on SASSLIB performances are systematically investigated. Surface lithium vacancies of NCM83 facilitate Li ion migration from SSE to NCM83 side, suppressing the H1 phase transformation of NCM83 and expanding the space charge layer. Surface Li_xNi_1−xO type rock salt phases inhibit oxygen-participating interfacial reactions at high voltages due to their low susceptibility to oxygen evolutions, enhancing the H2/H3 phase transformation of NCM83. Surface Li₂O and Li₂CO₃ mitigate the space charge layer effect and interfacial reactions at high voltages, activating H1 and H2/H3 phase transformations of NCM83. On the other hand, the combination of LiOH and Li₂CO₃ causes severe side reactions with SSE, resulting in escalated interfacial resistance and drastic capacity fading over cycling. Importantly, while the suppression of H1 and H2/H3 transformations reduces the reversible capacity, it mitigates the internal stress and micro-cracks in NCM83 particles, contributing to superior cycling stability of NCM83-sulfide ASSLIBs (94.1 % capacity retention over 500 cycles).

硫化物固体电解质（SSE）和富镍层状氧化物（NRLO）正极之间的界面相容性对于高性能硫化物全固态锂离子电池（SASSSLIBs）至关重要。然而，SASSLIBs 界面/容量退化的原因尚未明确解决。_{在此，系统地研究了LiNi 0.83} Co _0.11 Mn _0.06 O ₂ (NCM83)的表面结构和化学环境对SASSSLIB性能的影响。NCM83的表面锂空位促进了锂离子从SSE向NCM83侧迁移，抑制了NCM83的H1相变，扩大了空间电荷层。表面 Li _x Ni _1−xO 型岩盐相在高压下抑制氧参与界面反应，因为它们对氧析出的敏感性较低，从而增强了 NCM83 的 H2/H3 相变。表面 Li ₂ O 和 Li ₂ CO ₃减轻了高压下的空间电荷层效应和界面反应，激活了 NCM83 的 H1 和 H2/H3 相变。另一方面，LiOH 和 Li ₂ CO _3的结合与 SSE 引起严重的副反应，导致界面电阻升高和循环过程中容量急剧下降。重要的是，虽然抑制 H1 和 H2/H3 转变会降低可逆容量，但它减轻了 NCM83 颗粒中的内应力和微裂纹，有助于 NCM83-硫化物 ASSLIB 的出色循环稳定性（500 次循环后容量保持率达 94.1%）。