Morphology and Surface Reactivity Relationship in the LiMnO Spinel with x = 0.05 and 0.10: A Combined First-Principle and Experimental Study.

This article focuses on the surface reactivity of two spinel samples with different stoichiometries and crystal morphologies, namely LiMnO with x = 0.05 and 0.10. LiMnO compounds are good candidates as positive electrode of high-power lithium-ion batteries for portable devices. The samples were investigated using both experimental and theoretical approaches. On the experimental point of view, they were characterized in depth from X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS) analyses. Then, the reactivity was investigated through the adsorption of (SO) gaseous probes, in controlled conditions, followed by XPS characterization. First-principle calculations were conducted simultaneously to investigate the electronic properties and the reactivity of relevant surfaces of an ideal LiMnO material. The results allow us to conclude that the reactivity of the samples is dominated by an acido-basic reactivity and the formation of sulfite species. Nonetheless, on the x = 0.05 sample, both sulfite and sulfate species are obtained, the later, in lesser extent, corresponding to a redox reactivity. Combining experimental and theoretical results, this redox reactivity could be associated with the presence of a larger quantity of Mn cations on the last surface layers of the material linked to a specific surface orientation.