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The existence of a temperature-driven solid solution in LixFePO4 for 0 ≤ x ≤ 1

Nature Materials volume 4, pages 254–260 (2005)Cite this article

Abstract

Lithium-ion batteries have revolutionized the powering of portable electronics. Electrode reactions in these electrochemical systems are based on reversible insertion/deinsertion of Li+ ions into the host electrode material with a concomitant addition/removal of electrons into the host. If such batteries are to find a wider market such as the automotive industry, less expensive positive electrode materials will be required, among which LiFePO4 is a leading contender. An intriguing fundamental problem is to understand the fast electrochemical response from the poorly electronic conducting two-phase LiFePO4/FePO4 system. In contrast to the well-documented two-phase nature of this system at room temperature, we give the first experimental evidence of a solid solution LixFePO4 (0 ≤ x ≤ 1) at 450 °C, and two new metastable phases at room temperature with Li0.75FePO4 and Li0.5FePO4 composition. These experimental findings challenge theorists to improve predictive models commonly used in the field. Our results may also lead to improved performances of these electrodes at elevated temperatures.

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Figure 1: Projections of the triohylite LiFePO4 structure.
Figure 2: XRD patterns of LixFePO4 global compositions at 50 °C and 350 °C.
Figure 3: Temperature-controlled XRD patterns of two selected LixFePO4 global compositions under N2.
Figure 4: Unit-cell parameters as a function of x in LixFePO4 at 350 °C.
Figure 5: XRD patterns of quenched LixFePO4 (x = 0.8, 0.6, 0.4, 0.2) samples, from 400 °C to 25 °C.
Figure 6: Phase distribution diagrams of LixFePO4 (0 ≤ x ≤ 1) established from temperature-controlled XRD data.

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Acknowledgements

The authors express their sincere gratitude to D. Murphy and M. Touboul for helpful comments and discussions on this manuscript. They also thank UMICORE (Belgium) and C. Wurm for providing the pristine LiFePO4 powder.

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  1. Laboratoire de Réactivité et de Chimie des Solides, CNRS UMR 6007, Université de Picardie Jules Verne, 33 Rue St. Leu, Amiens, 80039 Cedex 9, France

    Charles Delacourt, Philippe Poizot, Jean-Marie Tarascon & Christian Masquelier

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Correspondence to Christian Masquelier.

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Delacourt, C., Poizot, P., Tarascon, JM. et al. The existence of a temperature-driven solid solution in LixFePO4 for 0 ≤ x ≤ 1. Nature Mater 4, 254–260 (2005). https://doi.org/10.1038/nmat1335

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