Phase transition of lithiated-spinel Li2Mn2O4 at high temperature

The phase transition of Li2Mn2O4 spinel at high temperature was investigated by XRD, TG/DTA, average oxidation state of Mn and cyclic voltammeric techniques. The results reveal that the Li2Mn2O4 spinel is unstable. At high temperature, it is easy to transform into [Li2−2x]tet[Mn2−xLix]octO4, which accompanies the formation of Li2MnO3 impurities. The phase transition is associated with the transfer of Li+ from tetrahedral 8a sites to octahedral 16d sites. With the increasing sintering temperature from 450 °C to 850 °C, the phase structure varies from lithiated-spinel Li2Mn2O4 to Li4Mn5O12-like to LiMn2O4-like and finally to rock-salt LiMnO2-like. In addition, a way of determining x with average oxidation state of Mn and the content of Li2MnO3 was also demonstrated.