Prediction of Li intercalation and battery voltages in layered vs. cubic LixCoO2

C. Wolverton*, Alex Zunger

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

98 Scopus citations

Abstract

It is now possible to use a quantum-mechanical electronic structure theory of solids and derive, completely from "first-principles," the voltage of a battery based on intercalation reaction energetics. Using such techniques, we investigate the structural stability, intercalation energies, and battery voltages of the two observed ordered phases ("layered" and cubic) of LiCoO2. We perform calculations for not only fully lithiated LiCoO2, but also fully delithiated □CoO2 and partially delithiated Li0.5CoO2. Our calculations demonstrate that removal of Li from the cubic phase results in movement of the Li atoms from their original octahedral sites to tetrahedral sites, forming a low-energy LiCo2O4 spinel structure. The energetics of the spinel phase are shown to account for the observed marked differences in battery voltages between the cubic and layered phases of LiCoO2. A small energy barrier exists for Li motion between octahedral and tetrahedral sites, thus indicating the metastability of the high-energy octahedral sites. Finally, we point out a possible pressureinduced layered → cubic transition in LiCoO2.

Original languageEnglish (US)
Pages (from-to)2424-2431
Number of pages8
JournalJournal of the Electrochemical Society
Volume145
Issue number7
DOIs
StatePublished - Jul 1998

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Renewable Energy, Sustainability and the Environment
  • Surfaces, Coatings and Films
  • Electrochemistry
  • Materials Chemistry

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