Composition and structure of acid leached LiMn2−yTiyO4 (0.2≤y≤1.5) spinels

Lithium manganese titanium spinels, LiMn2−yTiyO4, (0.2≤y≤1.5) have been synthesized by solid-state reaction between TiO2 (anatase), Li2CO3 and MnCO3. Li+ was leached from the powdered reaction products by treatment in excess of 0.2 N HCl at 85 °C for 6 h, under reflux. The elemental composition of the acidic solution and solid residues of leaching has been determined by complexometric titration, atomic absorption spectroscopy and X-ray fluorescence analysis. Powder X-ray diffraction was used for structural characterization of the crystalline fraction of the solid residues. It has been found that the amount of Li+ leached from LiMn2−yTiyO4 decreases monotonically with increasing y in the interval 0.2≤y≤1.0 and abruptly drops to negligibly small values for y>1.0. The content of Mn and Li in the liquid phase and of Mn and Ti in the solid (amorphous plus crystalline) residue, were related to the composition and cation distribution in the pristine compounds. A new formal chemical equation describing the process of leaching and a mechanism of the structural transformation undergone by the initial solids as a result of Li+ removal has been proposed.

Graphical abstractSchematic representation of the acid leaching of LiMn2−yTiyO4 (0.2≤y≤1.0).Figure optionsDownload full-size imageDownload as PowerPoint slide