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Because of the outstanding discharge capacity provided by oxygen redox activity, Li-rich layered oxide positive electrode materials for Li-ion batteries attract tremendous attention. However, there is still no full consensus on the role that the ionocovalency of transition metal (TM)–oxygen (O) chemical bonding plays in the reversibility of the oxygen redox as well as on both local crystal and electronic structure transformations. Here, we managed to tune the cationic/anionic redox contributions to the overall electrochemical activity using the xLi2RuO3-(1 – x)Li1.2Ni0.2Mn0.6O2 solid solutions as a model system possessing the same crystal structure and morphology as Li-rich layered oxides. We conclusively traced the whole cascade of events from increasing the covalency of the TM–O bond, suppressing irreversible oxygen oxidation to the generation of the reduced Mn species toward retarding the structure “densification” in the Li-rich layered oxides. The results demonstrate that enhancing the degree of covalency of the TM–O bonding is vitally important for anchoring the reversibility of the charge compensation mechanism occurring through partial oxygen oxidation.