Lithium transition-metal nitrides are promising anode candidates for Li-ion batteries. However, lithium must be extracted from the nitrides in an initial anodic oxidation, indicating these compounds cannot directly combine with the current cathodes to constitute cells. This deterrent can be overcome by introducing a certain amount of Co3O4, which shows large capacities and relatively high oxidation/reduction potentials, into the electrodes containing the above nitrides. A thermodynamically spontaneous reaction between these two active hosts results in a delithiated state of lithium metal nitrides. Under cycling within 1.4-0 V vs Li/Li+, Co3O4 is relatively inert to lithium and the nitrides become electrochemically active. The composite electrodes show high first-cycle efficiency of 100%, large capacities of 500 mAh g(-1), and excellent cyclability. Furthermore, research revealed that the composite electrodes demonstrated high cycling stability operating with polyethylene oxide (PEO) electrolytes at the elevated temperature. The reaction heating of the composite electrode under high Li utilization with PEO electrolytes via differential scanning calorimetry measurement was found to be extremely low compared with those of the lithium metal and the Li-alloy-based systems, suggesting that the composite electrodes could be promising anode candidates for all-solid-state PEO Li-ion batteries in terms of capacity, first-cycle charge efficiency, and thermal reliance. (c) 2006 The Electrochemical Society.