▎ 摘　　要

Reaction beyond intercalation and the utilization of metal ions beyond lithium-ions are two promising approaches for developing the next generation of high capacity and low cost energy storage materials. Here, we use graphene supported Co3O4 nanocubes and study their reaction with lithium, magnesium and aluminum using in situ transmission electron microscopy. On lithiation, the Co3O4 nanocubes decompose to Co metal nanoparticles (2 to 3 nm) and embed in as-formed Li2O matrix; conversely, the CoO nanoparticles form on the Co site accompanying the decomposition of Li2O in the delithiation process. The lithiation process is dominated by surface diffusion of Li+, and graphene sheets enhance the Li+ diffusion. However, upon charge with magnesium, the Mg2+ diffusion is sluggish, and there is no sign of conversion reaction between Mg and Co3O4 at room temperature. Instead, a thin film consisting of metal Mg nanoparticles is formed on the surface of graphene due to a process similar to metal plating. The Al3+ diffusion is even more sluggish and no reaction between Al and Co3O4 is observed. These findings provide insights to tackle the reaction mechanism of multivalent ions with electrode materials.