In Situ Conversion of Cu3P Nanowires to Mixed Ion/Electron‐Conducting Skeleton for Homogeneous Lithium Deposition

The introduction of 3D wettable current collectors is one of the practical strategies toward realizing high reversibility of lithium (Li) metal anodes, yet its effect is usually insufficient owing to single electron‐conductive skeleton. Here, homogeneous Li deposition behavior and enhanced Coulombic efficiency is reported for electrochemically lithiated Cu3P nanowires, owing to the formation of a mixed ion/electron‐conducting skeleton (MIECS). In particular, by evaluating the Gibbs free energy change, the possible chemical reaction between Cu3P and molten Li is used to construct a MIECS containing Li3P and Cu–Li alloy phase. The successful conversion of Cu3P nanowires to Li3P and Cu–Li alloy nanocomposite not only greatly reduces the surface energy between molten Li and Cu3P, but also induces uniform Li stripping/plating behavior via balanced ion/electron transport. Thus, the as‐obtained Li@MIECS composite anode displays superior cycling stability in both symmetric cells and full cells. This work provides a promising option for the preparation of high‐performance composite Li anodes containing MIECS by thermally pre‐storing Li.