A series of LiCrxMn2-xO4 spinels were synthesised by the Pechini method which enables dopant Cr ions to distribute at Mn sites homogeneously. Neutron diffraction and EDS analysis confirmed that Cr ions do occupy 16d sites (octahedral intestial) evenly in the spinel structure. The Cr dopant effect improves the cyclability of spinel LiMn2O4 electrodes and decreases the self-discharge rate substantially. Cyclic voltammetry and AC impedance spectroscopy were employed to characterise the reactions of lithium insertion into and extraction from LiCrxMn2-xO4 electrodes. It was found that a thicker surface layer was formed on the surface of the pure LiMn2O4 electrode than on the LiMn2O4 electrode.