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A first-order Mott transition in LixCoO2

Nature Materials volume 3, pages 627–631 (2004)Cite this article

Abstract

Despite many years of experimental searches for a first-order Mott transition in crystalline-doped semiconductors, none have been found. Extensive experimental work has characterized a first-order metal–insulator transition in LixCoO2, the classic material for rechargeable Li batteries, with a metallic state for x < 0.75 and insulating for x > 0.95. Using density functional theory calculations on large supercells, we identify the mechanism of this hereto anomalous metal–insulator transition as a Mott transition of impurities. Density functional theory demonstrates that for dilute Li-vacancy concentrations, the vacancy binds a hole and forms impurity states yielding a Mott insulator. The unique feature of LixCoO2 as compared with traditional doped semiconductors, such as Si:P, is the high mobility of the Li vacancies, which allows them to rearrange into two distinct phases at the temperature of the metal–insulator transition.

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Figure 1: A schematic of the density-of-states for various realizations of the impurity band.
Figure 2: LDA DOS for various supercells.
Figure 3: The total charge-density difference of Li0.969CoO2–CoO2.
Figure 4: Total energy of LixCoO2.

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Acknowledgements

This research was supported with funding from the Department of Energy Basic Energy Science contract DE-F602-96ER45571, the National Science Foundation (NSF) Materials Research Science and Engineering Center program, and NSF contract DMR-0096462. We also gratefully acknowledge computing resources from the National Partnership for Advanced Computational Infrastructure.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    C. A. Marianetti & G. Ceder

  2. Department of Physics and Astronomy, Center for Materials Theory, Rutgers University, Piscataway, 08854, New Jersey, USA

    G. Kotliar

  3. Center for Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    G. Ceder

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  1. C. A. Marianetti
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Correspondence to G. Ceder.

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Marianetti, C., Kotliar, G. & Ceder, G. A first-order Mott transition in LixCoO2. Nature Mater 3, 627–631 (2004). https://doi.org/10.1038/nmat1178

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