AN ELECTROCHEMICAL QUARTZ-CRYSTAL MICROBALANCE STUDY OF LITHIUM INSERTION INTO THIN-FILMS OF TUNGSTEN TRIOXIDE .1. MODELING OF THE IONIC INSERTION MECHANISM

A theoretical description of the mechanism of lithium insertion into amorphous thin films of tungsten trioxide (a-WO3) prepared by thermal vacuum evaporation of WO3 powder is presented. The model developed is based on the experimental results obtained by chronoamperometry and ac impedance spectroscopy associated with electrochemical quartz crystal microbalance (EQCM). The electrode mass change and the current flowing through the electrochemical cell during cathodic polarization are simultaneously recorded. As expected, it can be observed that the insertion process is associated with a gain of mass of the inserted electrode at long times (t > 1 s). On the other hand at short times (t < 1 s) a net loss of mass is observed. The existence of a non faradaic surface process involving the expulsion of anions from the electrode surface and occuring simultaneously with the faradaic insertion of non-solvated lithium ions into the oxide layer is discussed.