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.