(Fe,Cr)-binary oxide thin film electrodes were prepared as negative electrode material for lithium-ion micro-batteries by thermal growth on a stainless steel (AISI 410, FeCr12.5) current collector. The mechanisms of lithiation/delithiation were investigated by means of electrochemical (CV, galvanostatic cycling), spectroscopic (XPS, ToF-SIMS) and microscopic (SEM, AFM) analytical techniques. The as-prepared (Fe, Cr)-binary oxide electrodes exhibit a good cycling performance except the first discharge/charge cycle where a high irreversible capacity is observed due to formation of a solid electrolyte interphase (SEI) layer. The influence of substituting an oxidized iron by an oxidized chromium (CrxFe2-xO3 phase) was evaluated. The data show that the inferior electrochemical conversion activity of substituted oxidized chromium results in hindering lithium transport in the bulk thin film electrode. It was observed that the irreversible morphology modifications together with SEI evolution are critical to capacity degradation while retaining good coulombic efficiency. (C) 2015 Elsevier B.V. All rights reserved.