Ab initio calculation of the Li{sub x}CoO{sub 2} phase diagram

The electrochemical properties of the layered intercalation compound LiCoO{sub 2} used as a cathode in Li batteries have been investigated extensively in the past 15 years. Despite this research, little is known about the nature and thermodynamic driving forces for the phase transformations that occur as the Li concentration is varied. In this work, the phase diagram of Li{sub x}CoO{sub 2} is calculated from first principles for x ranging from 0 to 1. The calculations indicate that there is a tendency for Li ordering at x = 1/2 in agreement with experiment. At low Li concentration, the authors find that a staged compound is stable in which the Li ions selectively segregate to every other Li plane leaving the remaining Li planes vacant. They find that the two phase region observed at high Li concentration is not due to Li ordering and speculate that it is driven by a metal-insulator transition which occurs at concentrations slightly below x < 1.