A study of the ternary oxide LiVO2 and its anomalous behavior |
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| Affiliation: | 1. Department of Chemistry, University of Connecticut, Storrs, Connecticut 06268 USA;2. Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06268 USA;1. Division of Advanced Materials Engineering, Chonbuk National University, Jeonbuk 561-756, Republic of Korea;2. Hydrogen and Fuel Cell Research Center, Chonbuk National University, Jeonbuk 561-756, Republic of Korea;1. School of Chemistry, Institute of Science, Suranaree University of Technology, 30000, Thailand;2. Thermoelectric and Nanotechnology Research Center, Faculty of Science and Technology, Rajamangala University of Technology Suvarnabhumi, Asian Highway, Huntra Phranakhon Si Ayutthaya 13000, Thailand;3. Synchrotron Light Research Institute (Public Organization), 111 University Avenue, Muang District, Nakhon Ratchasima 30000, Thailand;1. Department of Emerging Materials Science, DGIST, Daegu 42988, Republic of Korea;2. School of Materials Science and Engineering, GIST, Gwangju 81005, Republic of Korea |
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| Abstract: | Nonstoichiometric LiVO2 and its unusual magnetic, electrical, and thermal phase transition near 200°C were studied using X-ray diffraction, IR and EPR spectroscopy, thermoanalytical methods, and measurements of electrical resistivity and magnetic susceptibility. The transition is semireversible, appearing to be noncooperative and of higher or multiple order. It has been concluded that the driving force for the transition is not a structural instability, but rather a critical distance phenomenon involving a change in the V3+V3+ bond type. The low-temperature data are interpreted in terms of a two-dimensional vanadium “metal cluster layer” formed via covalent-type metal-to-metal bonds; above Tt, narrow-band metallic behavior sets in within the vanadium planes. The phase transition in LiVO2 is similar to that of TiCl3, and is also very similar to the semiconducting-to-metallic transformations in VO2 and V2O3. |
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