The surface and bulk structure of the fully delithiated bare and AIPO(4)-coated LiCoO2 cathode materials (x = 0) between 200 and 400 degrees C were investigated using high resolution XRD, XAS (X-ray absorption spectroscopy), TEM, and solid-state NMR. Bare and coated CoO2 cathodes showed different phase transformation between 200 and 400 degrees C. The bare samples exhibited only the O1-CoO2 phase in the fully delithiated state, but the CoO2 phase was converted to the Co3O4 phase at higher temperatures. On the other hand, the AIPO(4)-coated LixCoO2 at x = 0 showed a mixture of phases including the major O1-type CoO2 and minor Co3O4 spinel phases in the fully delithiated state. When annealing temperatures increased from 200 to 400 degrees C, the bare samples showed a slow phase transition to Co3O4 and were completely transformed into the thermally stable Co3O4 spinel phase at 400 degrees C. The coated samples, however, were completely transformed into the spinel phase alone at 200 degrees C. We believe that the AIPO(4) coating layer accelerated the phase transition to the spinel phase at lower temperatures. TEM and XAS results showed that structural damages were mainly confined to the cathode particle surface, and this phenomenon was only observed in the bare samples. (c) 2007 Elsevier B.V. All rights reserved.