Electrochemical lithiation and passivation mechanisms of iron monosulfide thin film as negative electrode material for lithium-ion batteries studied by surface analytical techniques

摘要

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 voltam-metry, 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 Li_2FeS_2, 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 Li_2CO_3 with some presence of ROCO_2Li. 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.