Impact of thermal gas treatment on the surface modification of Li-rich Mn-based cathode materials for Li-ion batteries

High energy density Li-rich 0.33Li(2)MnO(3)& BULL;0.67LiNi(0.4)Co(0.2)Mn(0.4)O(2) (HE-NCM) layered structure cathodes for Li-ion batteries provide higher capacity gain via incorporation of an excess of lithium into the host. As a serious drawback, these cathodes suffer from continuous voltage fade upon cycling. Recently, high capacity retention, rate capability and low voltage hysteresis were achieved for HE-NCM by new thermal double gases SO2 and NH3 treatment. However, so far a fundamental understanding of the mechanisms responsible for this improved stability is missing. Herein, a comprehensive study of the chemical composition and electronic structure modifications of a series of HE-NCM (untreated, treated, carbon- and binder- free) is performed using advanced electron spectroscopy techniques supported by theoretical calculations. We demonstrate that the double gases treatment process leads to a partial reduction of Co3+ and Mn4+. The suggested chemical reactions include electron transfer from SO2, which behaves as a Lewis acid, to the transition metal sites accompanied by decomposition of SO2 and a characteristic surface modification which acts as protective layer for the HE-NCM.