Abstract
The electrochemical properties of the layered intercalation compound LiCoO2 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 LixCoO2 is calculated from first principles for x ranging from 0 to 1. Our calculations indicate that there is a tendency for Li ordering at x = 1/2 in agreement with experiment [1]. At low Li concentration, we 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. We 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.
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Acknowledgement
This work was supported by the Department of Energy, Office of Basic Energy Sciences under contract No. DEs-FG02s-96ER45571. We thank the San Diego Supercomputing Center for access to their C90 computers and the Center for Theoretical and Computational Materials Science of the National Institute of Science and Technology for generously providing us with computing resources. One of the authors (AVDV) gratefully acknowledges fellowship support from the DOE Computational Science Graduate Fellowship Program.
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Van Der Ven, A., Aydinol, M.K. & Ceder, G. Ab INITIO CALCULATION OF THE LixCoO2 PHASE DIAGRAM. MRS Online Proceedings Library 496, 121–126 (1997). https://doi.org/10.1557/PROC-496-121
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DOI: https://doi.org/10.1557/PROC-496-121