In summary, three kinds of radially oriented hierarchical architectures from tailorable V2O5 subunits of nanoribbons have been successfully shape-controlled fabricated through a facile hydrothermal method by simply varying the reagents. The species of alcohol and amount of urea both play a key role in the formation of final architectures. The morphology of subunits building shows regular changes, as transforming from nanoribbons to bundles by nanoribbons assembling along the side, then to curled wheat-leaf-like nanoribbons. A bundle oriented nucleation-growth-aggregation mechanism is proposed to understand the formation process of architectures. Owing to the superior structure of V2O5-II, when applied as cathode material for LIBs, the V2O5-II electrode material exhibit enhanced electrochemical performance, in both 2.0–4.0 V (157 mAh/g at 10 C) and 2.5–4.0 V (105 mAh/g at 40 C). The present work shows the potential application of radially oriented hierarchical architectures for high performance LIBs.
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