Can lithium form phases with molybdenum?

• Published in: Journal of solid state chemistry 2019-03, Vol.271, p.230-238
• Main Authors: Caputo, Riccarda, Tekin, Adem
• Format: Article
• Language: English
• Subjects: CASPESA; Crystal structure prediction; DFT calculations; Li-Mo phases; Lithiation of MoS2
• ISSN: 0022-4596; 1095-726X
• DOI: 10.1016/j.jssc.2018.12.057

Lithium and molybdenum do not form binary phases under thermodynamic control, but they might do under kinetic control upon lithiation of MoS2. High Lithiation of MoS2 can either lead to high-lithiated phases [1] or form Li-Mo phases at the lithiation point at which decomposition in Li2S and elemental molybdenum can occur. First-principles crystal structure prediction calculations suggest that the LiMo, monoclinic structure, and Li2Mo, either orthorhombic or tetragonal structures, can be formed under kinetic control as co-products of the overall process of lithiation of MoS2. The computed enthalpies of formation of the Li-Mo phases vary considerably if the long-range dispersion interactions are accounted in for the elemental lithium and molybdenum. High-lithiation of MoS2 can lead to the formation of kinetically controlled binary phases of Li-Mo. [Display omitted] •First-principles crystal structure prediction of Li-Mo system in the composition range of x in LixMo up to 3.•Two phases are found more stable than others: the monoclinic LiMo and orthorhombic Li2Mo phases.•The Li-Mo phases can be co-products of the lithiation reaction of MoS2.•The Li-Mo formation is favoured by the Mo-Mo interactions, which arrange in planar- and chain-like configurations.