We report the synthesis and electrochemical properties of highly stoichiometric LiNi1-zMzO2 (M = Co, Mn, Ti, z less than or equal to 0.3) samples. With the excess lithium method, samples with a well-defined layered structure can be prepared in air. A large rechargeable capacity of about 200 mAh g(-1) is obtained for 10% substitutives. Structural changes during charging and lithium ordering phenomena are discussed. We describe the thermal behavior of the substitutives and report the enhanced thermal stability and large rechargeable capacity of the manganese substitutives.