Understanding the Irreversible Reaction Pathway of the Sacrificial Cathode Additive Li6CoO4

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. Next‐generationsilicon anodes suffer from severe initial capacity loss. Antifluorite‐type Li6CoO4 can serve as an attractive sacrificial cathode additive by compensating for the irreversible capacity loss. A generalizable computational and experimental framework is presented to understand the lithium‐extraction pathway of Li6CoO4. The results provide insights on methods to redirect its reaction pathway to serve as a stable sacrificial cathode additive.