Construction of Hierarchical Nanotubes Assembled from Ultrathin V3S4@C Nanosheets towards Alkali‐Ion Batteries with Ion‐Dependent Electrochemical Mechanisms

Ultrathin core–shell V3S4@C nanosheets assembled into hierarchical nanotubes (V3S4@C NS‐HNTs) are synthesized by a self‐template strategy and evaluated as general anodes for alkali‐ion batteries. Structural/physicochemical characterizations and DFT calculations bring insights into the intrinsic relationship between crystal structures and electrochemical mechanisms of the V3S4@C NS‐HNTs electrode. The V3S4@C NS‐HNTs are endowed with strong structural rigidness owing to the layered VS2 subunits and interlayer occupied V atoms, and efficient alkali‐ion adsorption/diffusion thanks to the electroactive V3S4‐C interfaces. The resulting V3S4@C NS‐HNTs anode exhibit distinct alkali‐ion‐dependent charge storage mechanisms and exceptional long‐durability cyclic performance in storage of K+, benefiting from synergistic contributions of pseudocapacitive and reversible intercalation/de‐intercalation behaviors superior to those of the conversion‐reaction‐based Li+‐/Na+‐storage counterparts. V3S4@C in the shell: Ultrathin core–shell V3S4@C nanosheets assembled into hierarchical nanotubes are synthesized for alkali‐ion batteries. Alkali‐ion‐dependent charge storage mechanisms are put forward with systematic in situ/ex situ structural/physicochemical characterizations and DFT calculations.