Modulated and disordered phases in the system LiCdVO4-LiCd 4(VO4)3

E. Gaudin, H. Ben Yahia, F. J. Zúñiga, J. M. Pérez-Mato, J. Darriet

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Abstract

A solid solution (1 - x)LiCdVO4 - xLi1/3Cd 1/31/3CdVO4 has been observed for 0 ≤ x ≤ 1. From the cell parameters evolution, two domains of the solid solution have been distinguished with a discontinuity at x ≈ 0.6. The first one for 0 ≤ x ≤ 0.6 corresponds to the LiCdVO4 substructure of the Na2CrO4-type. For 0.75 ≤ x ≤ 1 satellite peaks are observed which correspond to a modulated structure. The first end-member LiCdVO4 (x = 0) crystallizes in Cmcm space group with a = 5.911, b = 8.975, and c = 6.513 Å. The structure consists of infinite edge-sharing chains of [CdO6] octahedra linked together by [VO4] tetrahedra and [LiO4] tetrahedra. According to the general formula Li1-2x/3Cdx/3x/3CdVO4 of the solid solution, when x increases cadmium replaces lithium in the [LiO 4] tetrahedra leading to [(Li/Cd/□)O4] disordered tetrahedra. All the phases in the domain 0.7 ≤ x ≤ 1 are one-dimensionally modulated with wavevector q = γc* and γ values of 0.75, 0.733, and 0.722 for x = 3/4, 6/7, and 9/10, respectively. The superspace group is Xmcm(00γ) where X stands for (1/2, 1/2, 0, 1/2) centering. The main structural result is a strong occupation modulation of lithium and cadmium in the tetrahedral site.

Original languageEnglish
Pages (from-to)2436-2447
Number of pages12
JournalChemistry of Materials
Volume17
Issue number9
DOIs
Publication statusPublished - 3 May 2005

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ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Gaudin, E., Yahia, H. B., Zúñiga, F. J., Pérez-Mato, J. M., & Darriet, J. (2005). Modulated and disordered phases in the system LiCdVO4-LiCd 4(VO4)3 Chemistry of Materials, 17(9), 2436-2447. https://doi.org/10.1021/cm050104e