Impedance behavior of the LiMn2O4/LiPF6-DMC-EC interface during cycling

Room temperature impedance measurements of the LiMn2O4/LiPF6-EC-DMC interface have been used to identify a previously unreported step in the formation of the SEI layer on this cathode. The low frequency impedance and potential of pure dense LiMn2O4 films was found to depend logarithmically on time in the end-of-discharge (EOD) state. The rate of the impedance rise decreased with Mn3+ content. The increased impedance was removed by oxidation of the film to 4.5 V vs. Li/Li+. The observations are consistent with a reversible disproportionation of part of the LiMn2O4 into Li2Mn2O4 and l-Mn2O4. Analyses of cyclic voltammograms and impedance spectra at intervals during constant current cycling of the LiMn2O4 films suggest that Li2Mn2O4 on the surface also plays a major role in the capacity fade