Relative stability of normal vs. inverse spinel for 3d transition metal oxides as lithium intercalation cathodes

Spinel oxides represent an important class of cathode materials for Li-ion batteries. Two major variants of the spinel crystal structure are normal and inverse. The relative stability of normal and inverse ordering at different stages of lithiation has important consequences in lithium diffusivity, voltage, capacity retention and battery life. In this paper, we investigate the relative structural stability of normal and inverse structures of the 3d transition metal oxide spinels with first-principles DFT calculations. We have considered ternary spinel oxides LixM2O4 with M = Ti, V, Cr, Mn, Fe, Co and Ni in both lithiated (x = 1) and delithiated (x = 0) conditions. We find that for all lithiated spinels, the normal structure is preferred regardless of the metal. We observe that the normal structure for all these oxides has a lower size mismatch between octahedral cations compared to the inverse structure. With delithiation, many of the oxides undergo a change in stability with vanadium in particular, showing a tendency to occupy tetrahedral sites. We find that in the delithiated oxide, only vanadium ions can access a +5 oxidation state which prefers tetrahedral coordination. We have also calculated the average voltage of lithiation for these spinels. The calculated voltages agree well with the previously measured and calculated values, wherever available. For the yet to be characterized spinels, our calculation provides voltage values which can motivate further experimental attention. Lastly, we observe that all the normal spinel oxides of the 3d transition metal series have a driving force for a transformation to the non-spinel structure upon delithiation.