The Li
+ ion diffusion coefficients (
DLi+) in V
2O
5 (2.12 × 10
−12 cm
2 s
−1) and in the intermediate α-, ε-, and δ-Li
xV
2O
5 phases (1.6 × 10
−14, 8.0 × 10
−15, and 8.5 × 10
−15 cm
2 s
−1, respectively), reversibly formed during charging/discharging processes of the crystalline-V
2O
5 and PEDOT (poly-3,4-ethylenedioxythiophene) composite-film electrode, are precisely determined by the galvanostatic intermittent titration technique. The specific surface area of the composite film is estimated to be 13.600 m
2 g
−1, where the external surface area and the nanopore area are 10.704 and 2.896 m
2 g
−1, respectively. The V
2O
5 crystals are coated and interconnected by a conductive polymer network in the composite film, thereby improving the electrode characteristics. V
2O
5 and PEDOT composite-film cathodes showed high specific capacities (290 mA h g
−1 at a 1 C rate), excellent rate capabilities (178 mA h g
−1 at a 10 C rate), and superior cycling stabilities (
ca. 15% degradation after 500 consecutive cycles).
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