Lithium dopant is introduced into lithium rich high capacity positive electrode active materials as a substitution for manganese within the complex metal oxides. In some embodiments, the lithium doped compositions can be written in a two component notation as x.Li2MnO3.(1−x)LiNiu+ΔMnu−Δ−dLidCowO2, where d ranges from about 0.004 to about 0.25 and 2u+w is approximately equal to 1. The materials are believed to form a layer-layer composite crystal structure that has very good cycling properties at high voltages, although the materials exhibit significant first cycle irreversible capacity loss.