A High‐Rate V2O5 Hollow Microclew Cathode for an All‐Vanadium‐Based Lithium‐Ion Full Cell

V₂O₅ hollow microclews (V₂O₅‐HMs) have been fabricated through a facile solvothermal method with subsequent calcination. The synthesized V₂O₅‐HMs exhibit a 3D hierarchical structure constructed by intertangled nanowires, which could realize superior ion transport, good structural stability, and significantly improved tap density. When used as the cathodes for lithium‐ion batteries (LIBs), the V₂O₅‐HMs deliver a high capacity (145.3 mAh g^‐1) and a superior rate capability (94.8 mAh g^‐1 at 65 C). When coupled with a lithiated Li₃VO₄ anode, the all‐vanadium‐based lithium‐ion full cell exhibits remarkable cycling stability with a capacity retention of 71.7% over 1500 cycles at 6.7 C. The excellent electrochemical performance demonstrates that the V₂O₅‐HM is a promising candidate for LIBs. The insight obtained from this work also provides a novel strategy for assembling 1D materials into hierarchical microarchitectures with anti‐pulverization ability, excellent electrochemical kinetics, and enhanced tap density.