Staging Phase Transitions in Li[sub x]CoO[sub 2]

Recently, there has been more and more interest in charging to potentials above 4.2 V to increase its specific capacity for commercial use. Unlike the situation for below 4.2 V, the electrochemistry and structure of above 4.2 V is not completely clear. In this study, two reversible plateaus at 4.55 and 4.63 V were observed in the voltage profile of cells, which were then studied by in situ X-ray diffraction (XRD). The intermediate phase, formed at 4.6 V with in was determined to be a stage two phase, that is with lithium occupying only every second space between "sandwiches." The structure of this phase was determined using Rietveld refinement of an ex situ XRD pattern of We find that adjacent sandwiches are stacked with aa transition metal alignments if there are no Li atoms between them (as in and with ab alignments if there are Li atoms between them (as in This leads to a six-layer unit cell. The structure we find agrees well with that predicted by Ceder's group for the stage two phase that they call H1-3. © 2002 The Electrochemical Society. All rights reserved.