The lithiation/delithiation reaction mechanism of iron monosulfide (troilite Fe(1-x)S, x = 0.07) as negative electrode material for lithium-ion batteries and the electrode passivation induced by reductive decomposition of the electrolyte were studied by combining surface (X-ray photoelectron spectroscopy, XPS, and time-of-flight secondary ion mass spectrometry, ToF-SIMS) and electrochemical analysis (cyclic voltammetry, CV) of thin films grown by thermal sulfidation of metal iron substrate. XPS analysis performed at different stages of the first lithiation/delithiation cycle shows that the reversible formation of metallic iron and lithium sulfide is not solely limited to the principal cathodic/anodic peaks at 1.23/1.89 V and that disulfide products, possibly Li2FeS2, are also formed at lower cathodic potentials. ToF-SIMS depth profiling of the thin film electrode confirms an incomplete process of conversion/deconversion and reveals an expansion/shrinkage of the material induced by electrochemical lithiation/delithiation. The solid electrolyte interphase (SEI) layer formed on the iron monosulfide thin film electrode is mostly composed of Li2CO3 with some presence of ROCO2Li. For the first time, it is shown that the SEI layer thickness varies upon conversion/deconversion, between 9 and 4.5 nm in the lithiated and delithiated states, respectively, on a conversion-type electrode. Moreover, the electrolyte decomposition products penetrate the bulk electrode until the current collector owing to pulverization/cracking caused by expansion and shrinkage of the thin film material upon cycling. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.