Using LiI as the reducing agent, the compound O2-Li(2/3)+x (Ni1/3Mn2/3)O-2, x similar to 1/3 (O2(Li+x)) has been prepared from the O2-Li-2/3 (Ni1/3Mn2/3)O-2 (O2(Li)). Cyclic voltammetry and voltage-capacity profiles of the O2(Li+x) phase are qualitatively different from that of O2(Li) phase. The first extraction capacity of O2(Li +x) at C/10 rate is 190 mAh/g corresponding to the removal of 2/3 mole of Li from the compound. At C/5 rate it delivers a reversible capacity of 158 mAh/g at 25 C and 184 mAh/g at 50 C (vs Li metal; voltage window 2.5-4.6 V). In Li-ion cells, with MCMB anode and O2(Li + x) as cathode, a discharge capacity of 140 mAh/g was obtained at C/5 rate in the voltage window 2.5-4.5 V (25 degreesC). The charge-discharge cycling performance and the cyclic voltammograms reveal that O2(Li) and O2(Li + x) do not convert to the spinel structure. (C) 2002 Published by Elsevier Science B.V.