Several new compounds, with desirable properties of ion mobility and working voltage, have been recently proposed using a density functional theory (DFT) computational approach as potential electrode materials for beyond-lithium battery systems. After evaluation of the ‘energy above hull’, thiospinel MgCr2S4 has been suggested as interesting multivalent battery cathode candidate, even though the synthesis of its exact stoichiometry poses serious challenges. In this work, MgCr2S4 is prepared using an innovative mechanochemical route starting from magnesium or magnesium hydride, chromium, and sulfur powders. The progress of such mechanically induced reaction as a function of processing time is carefully monitored by XRD with Rietveld refinement, evidencing the occurrence of a mechanically induced self-propagating reaction (MSR). The effect of parameters associated with the milling apparatus (impact energy) on the products composition are also investigated. To our knowledge, this work represents the first report of the scalable and simple mechanical alloying synthesis of thiospinel MgCr2S4 (space group Fd-3 m, a = 10.09 Å) and opens up interesting possibilities for the exploitation of such material in next-generation post-lithium batteries.

In situ synchrotron and conventional XRD patterns were solved for the phase developed at 700 °C with the Amm2 orthorhombic space group, lattice parameters a = 21.187 Å; b = 3.827 Å; c = 19.377 Å; β = 119.83° and chemical composition V4Nb20O60 (ρ = 4.09 g cm−3).