In the development of Li-ion batteries for electric vehicles (EVs), Ni-rich layered oxides are anticipated to be promising cathode materials. However, the rapid capacity fading originating from microcracks has prevented practical applications of Ni-rich cathodes. Herein, we systematically perform post-mortem analyses of Li[Ni x Co y Mn 1-x-y ]O 2 (x = 0.8 and 0.9) cathodes after long-term cycling, focusing on the particle interior. The results demonstrate that microcracks and the resultant degradation of the secondary particle interior by exposure to the deleterious electrolyte are dominant factors in the deterioration of Ni-rich cathodes. Moreover, cathode degradation significantly decreases the ionic and electrical conductivities, leading to the partial electrochemical insulation inside the cathode particles. This insulation contributes to the kinetic loss of capacity at high C-rates and induces structural inhomogeneity in the cathode. A comprehensive understanding of the degradation mechanism of Ni-rich cathodes suggests guidelines for developing Ni-rich cathode materials that are appropriate for application in EVs.

The use of a sacrificial cathode additive that contains a large amount of lithium is one potential solution to compensate for the irreversible capacity loss associated with next‐generation anodes such as silicon. Antifluorite‐type Li6CoO4 has attracted attention as a potential cathode additive owing to its remarkably high theoretical lithium extraction capacity. However, the complex mechanism of lithium extraction as well as the oxygen loss from Li6CoO4 is not well understood. A generalizable computational thermodynamics and experimental framework is presented to understand the lithium‐extraction pathway of Li6CoO4. It is found that one lithium per formula unit can be topotactically extracted from Li6CoO4, followed by an irreversible and nontopotactic phase transformation to Li2CoO3 or LiCoO2 depending on the temperature. The results show that peroxide species may form to charge‐compensate for Li extraction which is undesirable as this can lead to gas release during battery operation. It is suggested that charging Li6CoO4 at an elevated temperature that the electrolyte can withstand, redirects the reaction pathway and prevents the formation of intermediate peroxide species making it an effective and stable sacrificial cathode additive.

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