Pure and substituted spinels, LiM1/6Mn11/6O4 (M = Co, (Co,Al), (Co,Cr), (Cr,Al)), were prepared, characterised by X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS) and their cathodic performance evaluated. The Mn 2P(3/2) XPS analysis shows a decrease in Mn3+ concentration by substitution. The cyclic voltammograms and the charge-discharge profiles of the M-substituted compounds show an indication of structural stabilisation, a decrease in the values of charge and discharge capacities, but a considerable improvement of capacity retention at room temperature as well as at 50 degreesC.