Analysis of cyclic voltammograms of electrochromic a-WO3 films from voltage-dependent equilibrium capacitance measurements

The main features of cyclic voltammograms (CVs) of thin electrochromic films based on a-WO₃ were investigated. First, the chemical capacitance is defined in terms of the electrochemical potential variation with the insertion level, x, and is measured under galvanostatic (chronopotentiometry) quasi-equilibrium conditions. An equilibrium capacitance increasing rapidly with respect to insertion level or negative potential is observed, respectively C_ch∝x^a at x>10^?3(a≈0.74) and C_ch∝V^α(α≈3). Simulation methods used to generate the observed CVs are described in detail. Major CV peaks can be simply understood as charging and discharging of the variable capacitor, in conjunction with a distortion of the voltage scale due to a series transport process. Therefore a simple RC equivalent circuit allows us to explain the principal CVs characteristics of lithium intercalation and deintercalation in amorphous films.