Journal
SOLID STATE IONICS
Volume 180, Issue 40, Pages 1613-1619Publisher
ELSEVIER
DOI: 10.1016/j.ssi.2009.11.010
Keywords
Lithium ion conductors; Nasicon snucture; Li-7 and P-31 MAS-NMR spectroscopy; Electric impedance spectroscopy
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Funding
- Spanish Agency CICYT [MAT2007-64486-CO7]
- Regional Government of Madrid [S-505/PPQ-0358]
- Spanish Ministry of Science and Innovation
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Materials of the LiTi2-xZrx(PO4)(3) series (0 <= x <= 2) were prepared and characterized by powder X-ray (XRD) and neutron diffraction (ND), Li-7 and P-31 Nuclear Magnetic Resonance (NMR) and Electric Impedance techniques. In samples with x<1.8, XRD patterns were indexed with the rhombohedral R3c space group, but in samples with x >= 1.8, XRD patterns display the presence of rhombohedral and triclinic phases. The Rietveld analysis of the LiTi1.4Zr0.6(PO4)(3) neutron diffraction (ND) pattern provided structural information about intermediate compositions. For low Zr contents, compositions deduced from, P-31 MAS-NMR spectra are similar to nominal ones, indicating that Zr4+ and Ti4+ cations are randomly distributed in the NASICON structure. At increasing Zr contents, differences between nominal and deduced compositions become significant, indicating some Zr segregation in the triclinic phase. The substitution Ti4+ by Zr4+ stabilizes the rhombohedral phase: however, electrical performances are not improved in expanded networks of Zr-rich samples. Below 300 K, activation energy of all samples is near 0.36 eV; however, above 300 K, activation energy is near 0.23 eV in Ti-rich samples and close to 0.36 eV in Zr-rich samples. The analysis of electrical data suggests that the amount of charge carriers and entropic terms are higher in Zr-rich samples: however, the increment of both parameters does not compensate lower activation energy terms of these samples. As a consequence of different contributions, the bulk conductivity of Zr-rich samples, measured at room temperature, is one order of magnitude lower than that measured in Ti-rich samples. (C) 2009 Elsevier B.V. All rights reserved.
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