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Room-temperature single-phase Li insertion/extraction in nanoscale LixFePO4

Nature Materials volume 7, pages 741–747 (2008)Cite this article

Abstract

Classical electrodes for Li-ion technology operate by either single-phase or two-phase Li insertion/de-insertion processes, with single-phase mechanisms presenting some intrinsic advantages with respect to various storage applications. We report the feasibility to drive the well-established two-phase room-temperature insertion process in LiFePO4 electrodes into a single-phase one by modifying the material’s particle size and ion ordering. Electrodes made of LiFePO4 nanoparticles (40 nm) formed by a low-temperature precipitation process exhibit sloping voltage charge/discharge curves, characteristic of a single-phase behaviour. The presence of defects and cation vacancies, as deduced by chemical/physical analytical techniques, is crucial in accounting for our results. Whereas the interdependency of particle size, composition and structure complicate the theorists’ attempts to model phase stability in nanoscale materials, it provides new opportunities for chemists and electrochemists because numerous electrode materials could exhibit a similar behaviour at the nanoscale once their syntheses have been correctly worked out.

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Figure 1: XRD patterns of S40 and S140 nanosized LiFePO4.
Figure 2: Characterization of the 40 nm nanosized LiFePO4 sample.
Figure 3: Rietveld refinement of the 40 nm (S40) nanosized LiFePO4.
Figure 4: Electrochemical characterizations of the 40 nm (S40) LiFePO4 and carbon-coated nano-LiFePO4.
Figure 5: Electrochemical and structural characterization of the 40 nm (S40) LiFePO4.
Figure 6: Unit-cell parameters as a function of x lithium extracted in 40 nm (S40) nanosized LixFePO4.

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Acknowledgements

We are grateful to C. Delacourt and D. W. Murphy for enlightening discussions and to J. Rodriguez Carvajal at ILL Grenoble for his help in collecting the neutron diffraction patterns.

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Authors and Affiliations

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

    Pierre Gibot, Montse Casas-Cabanas, Lydia Laffont, Stéphane Hamelet, Jean-Marie Tarascon & Christian Masquelier

  2. UMICORE Research & Development, Kasteelstraat 7, B-2250 Olen, Belgium

    Stephane Levasseur & Philippe Carlach

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  1. Pierre Gibot
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Correspondence to Christian Masquelier.

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Supplementary Figures S1–S2 & Tables S1–S2 (PDF 1191 kb)

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Gibot, P., Casas-Cabanas, M., Laffont, L. et al. Room-temperature single-phase Li insertion/extraction in nanoscale LixFePO4. Nature Mater 7, 741–747 (2008). https://doi.org/10.1038/nmat2245

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