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Flux crystal growth and thermal stabilities of LiV2O4

Nature Materials volume 4, pages 845–850 (2005)Cite this article

Abstract

The spinel oxide LiV2O4 is a interesting compound that shows heavy fermion behaviour despite its d-electron system. The large quasiparticle specific heat coefficient (γ value) is close to those of other heavy fermion systems in f-electron Zintl compounds. The mechanism of such heavy fermion behaviour in LiV2O4 has not been resolved, owing to the lack of high-quality single crystals required for experiments. Here we present a crystal-growth technique for LiV2O4 using a solvent system that acts effectively for mixed-valence vanadium (V3+ and V4+) oxides. The grown crystals have a well-developed octahedral form bounded by {111} faces, with high crystallographic quality and maximum size of almost 1.0×1.0×1.0 mm. The crystals have stoichiometric composition and show heavy fermion behaviour with an extremely large γ value of ∼460 mJ mol−1 K−2. Crystals of LiV2O4 are very sensitive to air and moisture, but are stable up to 1,020 ∘C under vacuum.

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Figure 1: Temperature dependence of LiV2O4 solubility in LiCl-Li2MoO4-LiBO2 flux system.
Figure 2: Scanning electron micrograph of grown LiV2O4 single crystals with 1.0x1.0x1.0 mm size in the cross edge direction.
Figure 3: Physical properties of grown LiV2O4 crystals.
Figure 4: Lithium-ion channels in LiV2O4 structure.
Figure 5: Temperature dependence of the thermal weight change of LiV2O4 crystals under air.

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Acknowledgements

The authors thank M. Koike for help in the early stage of this work, Z. Hiroi for specific heat measurements, T. Kitazawa for his help in the crystal-growth experiments, F. Sakai for the chemical analyses, J. Yamaura for single-crystal X-ray diffraction measurements using a CCD diffractometer and G. Heale for critical reading. This work is partly supported by Grants-in-Aid for Scientific Research (Nos 407 and 758) and for Creative Scientific Research (No. 13NP0201) from the Ministry of Education, Culture, Sports, Science, and Technology. We also gratefully acknowledge Komatsu Ltd. Co. for financial support.

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  1. Materials Design and Characterization Laboratory (MDCL), Institute for Solid State Physics (ISSP), The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba, 277-8581, Japan

    Yoshitaka Matsushita, Hiroaki Ueda & Yutaka Ueda

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  1. Yoshitaka Matsushita
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Correspondence to Yoshitaka Matsushita or Yutaka Ueda.

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Matsushita, Y., Ueda, H. & Ueda, Y. Flux crystal growth and thermal stabilities of LiV2O4. Nature Mater 4, 845–850 (2005). https://doi.org/10.1038/nmat1499

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