Orthorhombic LiMnO2 (o-LiMnO2) thin films were produced by non-reactive r.f. magnetron sputtering in combination with thermal post-annealing. Oxide phase formation was investigated by X-ray diffraction and Raman spectroscopy. In order to assign the X-ray signals and estimate the grain size, a simulation of the diffraction pattern was performed and compared with experimental data. The density of the films was determined to be 3.39 g/cm(3) using X-ray reflectivity. Electrochemical characterization was carried out by galvanostatic cycling and cyclic voltammetry of Li/o-LiMnO2 half cells. There are distinct redox reactions at approx. 3 V and 4 V, whereas the latter splits into multiple peaks. Using ab initio calculations and thermodynamic models, Gibbs energies of o-LiMnO2 and c-LiMn2O4 were determined. The relation between these energies explains the irreversible phase transformation that has been observed during the cycling of the Li/o-LiMnO2 half cell. (C) 2013 Elsevier B.V. All rights reserved.