Correlation between volume change and cell voltage variation with composition for lithium intercalated amorphous films

Interactions between the intercalant and the host have been studied in homogeneous amorphous LixWO3 prepared by electron beam evaporation, using electrochemical experiments with films of different thickness (100-400 nm). We have related the intercalation thermodynamics, described previously by us [Solid State Ionics 2005, 176, 1701] with other models that take into account film volume dilatation along the intercalation. A distinct behavior of cell voltage variation with composition and volume change is observed for the thinnest (100 nm) films: cell voltage follows ideal insertion thermodynamics and no deformation was detected using profilometry techniques. In contrast, thicker films exhibited both volume changes and, correspondingly, cell voltage departs from ideality due to contributions to the chemical potential arising from elastic distortions of the host matrix.