Understanding structural evolution in lithium-rich layered oxidized composites (LLO) is fundamental to design improved cathode materials for rechargeable lithium-ion batteries (LIBs). In particular, retrieving quantitative structural parameters are essential factors to unveil the hidden phases or atomic orderings affecting the properties of LIBs. The oxygen-vacancies heterogeneity is revealed in 0.5Li₂MnO₃·0.5LiNi_1/3Co_1/3Mn_1/3O₂ (LR-NCM) during de-lithiation process via rigid structural refinements. Through the in-situ/ex-situ X-ray absorption spectroscopy (XAS) in synergy with first principles calculations, the dynamic structural (and electronic) evolution of oxygen vacancies is confirmed to be in the form of MnO₂ (represents vacancy site) for Li₂MnO₃ component. With the formation of oxygen vacancies in Li₂MnO₃ component, the oxygen-vacancy-bearing structure MnO₂ also play significant supporting role on its parent structure without obvious Mn ions activity. This result offers new perspectives on synergistic improvement in the electronic and structural evolution, which is the key to design high energy density cathode materials for next-generation lithium ion batteries.

了解富锂层状氧化复合材料（LLO）的结构演变是设计用于可充电锂离子电池（LIB）的改进阴极材料的基础。特别是，检索定量结构参数是揭示影响LIBs性质的隐藏相或原子序的必不可少的因素。通过刚性结构改进，在去锂化过程中0.5Li ₂ MnO ₃ ·0.5LiNi _1/3 Co _1/3 Mn _1/3 O ₂（LR-NCM）揭示了氧空位异质性。通过原位/异位X射线吸收光谱法（XAS）与第一原理计算协同作用，证实了氧空位的动态结构（和电子）演变为Li ₂ MnO ₃组分的MnO ₂形式（代表空位）。随着Li ₂ MnO ₃组分中氧空位的形成，含氧空位结构MnO ₂在其母体结构上也起着重要的支撑作用，而Mn离子活性却不明显。该结果为电子和结构演变的协同改进提供了新的观点，这是设计用于下一代锂离子电池的高能量密度阴极材料的关键。