Sol–gel preparation of cobalt manganese mixed oxides for their use as electrode materials in lithium cells

Abstract

An ethanol dehydration procedure has been used to precipitate gel-like citrate precursors containing cobalt and manganese transition metal ions. Further annealing led to the Mn x Co 3− x O 4 spinel oxide series ( x: 1, 1.5, 2, 3). Annealing temperature and treatment time were also evaluated to optimize the performance of the oxides as active electrode materials in lithium cells. The manganese–cobalt mixed oxides obtained by this procedure were cubic or tetragonal phases depending on the cobalt content. SEM images showed spherical macroporous aggregates for MnCo 2O 4 and hollow spheres for manganese oxides. The galvanostatic cycling of lithium cells assembled with these materials demonstrated a simultaneous reduction of cobalt and manganese during the first discharge and separation of cobalt- and manganese-based products on further cycling. As compared with binary manganese oxides, a notorious electrochemical improvement was observed in the mixed oxides. This behavior is a consequence of the synergistic effect of both transition metal elements, associated with the in-situ formation of a nanocomposite electrode material when cobalt is introduced in the manganese oxide composition. Values higher than 400 mAh/g were sustained after 50 cycles for MnCo 2O 4.