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

Ultrathin core-shell V₃ S₄ @C nanosheets assembled into hierarchical nanotubes (V₃ S₄ @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 V₃ S₄ @C NS-HNTs electrode. The V₃ S₄ @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 V₃ S₄ -C interfaces. The resulting V₃ S₄ @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.