| Summary: | V<sub>6</sub>O<sub>13</sub> thin films were deposited on indium-doped tin oxide (ITO) conductive glass by a concise low-temperature liquid-phase deposition method and through heat treatment. The obtained films were directly used as electrodes without adding any other media. The results indicate that the film annealed at 400 °C exhibited an excellent cycling performance, which remained at 82.7% of capacity after 100 cycles. The film annealed at 400 °C with diffusion coefficients of 6.08 × 10<sup>−12</sup> cm<sup>2</sup>·s<sup>−1</sup> (Li<sup>+</sup> insertion) and 5.46 × 10<sup>−12</sup> cm<sup>2</sup>·s<sup>−1</sup> (Li<sup>+</sup> extraction) in the V<sub>6</sub>O<sub>13</sub> film electrode. The high diffusion coefficients could be ascribed to the porous morphology composed of ultrathin nanosheets. Moreover, the film endured phase transitions during electrochemical cycling, the V<sub>6</sub>O<sub>13</sub> partially transformed to Li<sub>0.6</sub>V<sub>1.67</sub>O<sub>3.67</sub>, Li<sub>3</sub>VO<sub>4</sub>, and VO<sub>2</sub> with the insertion of Li<sup>+</sup> into the lattice, and Li<sub>0.6</sub>V<sub>1.67</sub>O<sub>3.67</sub>, Li<sub>3</sub>VO<sub>4</sub>, and VO<sub>2</sub> partially reversibly transformed backwards to V<sub>6</sub>O<sub>13</sub> with the extraction of Li<sup>+</sup> from the lattice. The phase transition can be attributed to the unique structure and morphology with enough active sites and ions diffusion channels during cycles. Such findings reveal a bright idea to prepare high-performance cathode materials for LIBs.
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