| Summary: | The open-layered structure of Vanadium pentoxide (V<sub>2</sub>O<sub>5</sub>) has triggered significant interest in exploring its energy-related application as lithium (Li) intercalation cathode material. Various methods are extensively studied to improve the Li diffusion using thin films or nanoarchitecture. In this work, high-quality two-dimensional (2D) inverse opal α-V<sub>2</sub>O<sub>5</sub> films were synthesized via a modified ‘dynamic hard template’ infiltration strategy using sacrificial polystyrene spheres (PS, a diameter of 530 nm) photonic crystal as a template. The new material exhibited an excellent porous array with featured structural colors in a large area. The electrochromic behavior was explored by combining bandgap and electrochemical characterization. On the one hand, the intercalation/deintercalation of Li<sup>+</sup> played an important role in the bandgap (Eg), and thereafter on the visible range transmittance through changing the film’s stoichiometry and the valence of vanadium ions. On the other hand, the asymmetry of the lattice due to the disordered distribution of Li<sup>+</sup> within the V<sub>2</sub>O<sub>5</sub> interlayer and/or the formation of an irreversible phase explained the change in transmittance with voltage.
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