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[Display omitted] The Li-rich layered oxide is considered as one of the most promising cathode materials for high energy density batteries, due to its ultrahigh capacity derived from oxygen redox. Although incorporating over-stoichiometric Li into layered structure can generate Li 2 MnO 3 -like domain and enhance the oxygen redox activity thermodynamically, the fast and complete activation of the Li 2 MnO 3 -like domain remains challenging. Herein, we performed a systematic study on structural characteristics of Li-rich cathode materials to decipher the factors accounting for activation of oxygen redox. We reveal that the activation of Li-rich cathode materials is susceptible to local Co coordination environments. The Co ions can intrude into Li 2 MnO 3 -like domain and modulate the electronic structure, thereby facilitating the activation of Li-rich layered cathode materials upon first charging, leading to higher reversible capacity. In contrast, Li 2 MnO 3 -like domain hardly contains any Ni ions which contribute little to the activation process. The optimum composition design of this class of materials is discussed and we demonstrate a small amount of Co/Mn exchange in Li 2 MnO 3 -like domain can significantly promote the oxygen redox activation. Our findings highlight the vital role of Co ions in the activation of oxygen redox Li-rich layered cathode materials and provide new insights into the pathway toward achieving high-capacity Li-rich layered cathode materials. [ABSTRACT FROM AUTHOR]

[Display omitted] Classical layered transition metal oxides have remained the preferred cathode materials for commercial lithium-ion batteries. Variation in the transition metal composition and local ordering can greatly affect the structure stability. In classical layered cathodes, high concentrations of electrochemically inert Mn elements usually act as a pillar to stabilize the structure. When excess amount of Li and Mn are present in the layered structure, the capacity of the Li-rich layered oxide (molar ratio of lithium over transition metal is larger than one by design) can exceed that expected from transition metal redox. However, the over lithiation in the classical layered structure results in safety issues, which remains challenging for the commercialization of Li-rich layered oxides. To characterize the safety performance of a series of Li-rich layered cathodes, we utilize differential scanning calorimeter and thermal gravimetric analysis; this is coupled with local structural changes using in situ temperature dependent synchrotron X-ray diffraction and X-ray adsorption spectroscopy. These methods demonstrate that the gradual decrease of the Mn–M (M = Ni, Co, Mn and Li) coordination number directly reduces structural stability and accelerates oxygen release. For safety characterization tests in practice, we evaluate the thermal runaway process through accelerating rate calorimeter in 1.0 Ah pouch cells to confirm this trend. Using the insights obtained in this work, we design a polymorphic composition to improve the thermal stability of Li-rich layered cathode material, which outperforms Ni-rich layered oxides in terms of both electrochemical and safety performances. [ABSTRACT FROM AUTHOR]