Electrochemical lithium intercalation in nanosized manganese oxides

X-ray amorphous manganese oxides were prepared by reduction of sodium permanganate by lithium iodide in aqueous medium (MnOx-I) and by decomposition of manganese carbonate at moderate temperature (MnOx-C). TEM showed that these materials are not amorphous, but nanostructured, with a prominent spinel substructure in MnOx-C. These materials intercalate lithium with capacities up to 200 mAh/g at first cycle (potential window 1.8-4.3 V) and 175 mAh/g at 100th cycle. Best performances for MnOx-C are obtained with cobalt doping. Potential electrochemical spectroscopy shows that the initial discharge induces a 2-phase transformation in MnOx-C phases, but not in MnOx-I ones. EXAFS and XANES confirm the participation of manganese in the redox process, with variations in local structure much smaller than in known long-range crystallized manganese oxides. X-ray absorption spectroscopy also shows that cobalt in MnOx-C is divalent and does not participate in the electrochemical reaction.