Phase Transformation of Lithium‐rich Oxide Cathode in Full Cell and its Suppression by Solid Electrolyte Interphase on Graphite Anode

Lithium‐rich oxide is one of the most promising cathodes that meet high energy density requirement for batteries of the future, but its phase transformation from layer to spinel structure caused by the lattice instability presents severe challenge to cycling stability and the actually accessible capacity. The currently available approaches to suppress this undesired irreversible process often resort to limit the high voltages that lithium‐rich oxide is exposed to. However, cycling stability thus improved is at the expense of the eventual energy output. In this work, we identified a new mechanism that is directly responsible for the lithium‐rich oxide phase transformation and established a clear correlation between the successive consumption of Li + on anode due to incessant interphase repairing and the over‐delithiation of lithium‐rich oxide cathode. This new mechanism enables a simple but effective solution to the cathode degradation, in which an electrolyte additive is used to build a dense and protective interphase on anode with the intention to minimize Li depletion at cathode. The application of this new interphase effectively suppresses both electrolyte decomposition at anode and the phase transformation of lithium‐rich oxide cathode, leading to high capacity and cycling stability.