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Significance Statement
Alkali-ion conductive oxide glass materials have been attracting great interest as alternatives to conventional organic liquid or gel electrolytes because of the safety properties of solid state batteries. In this study, the structural characterization for NASICON (Na+ Super Ionic Conductor)-type glass ceramics of SiO2-P2O5-ZrO2-R2O (R=Na, Li) was investigated to clarify the better conductive mechanism of Li-glass ceramics than that of Na-glass ceramics by synchrotron X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS). The Debye-Waller factors related to the oxygen surrounding the Zr ion for the Li-glass ceramics were higher than those for the Na-glass ceramics. The static disorder around Zr ion may cause more weakly bonding between the Li ions and surrounding atoms, resulting in the improvement of ionic conductivity.
Journal Reference
Journal of Materials Science, December 2015, Volume 50, Issue 23, pp 7735-7741
Tomoyuki Tsujimura
[expand title=”Show Affiliations”]Research Center, Asahi Glass Co., Ltd., 1150 Hazawa-cho, Kanagawa-ku, Yokohama, 221-8755, Japan.
[/expand]Abstract
The structural characterization for Na+ Super Ionic Conductor (NASICON)-type glass ceramics of 20R2O–XZrO2–15P2O5–(65-X)SiO2 (R = Na, Li) was investigated by X-ray diffraction (XRD) and X-ray absorption fine structure to clarify the better conductive mechanism of Li-glass ceramics than that of Na-glass ceramics. The Na-glass ceramics were synthesized by heat treatment using glass material, and the Li-glass ceramics were obtained through ion exchange techniques from Na-glass ceramics. From the XRD analysis, the positive correlation between ionic conductivity and lattice parameter was identified for the Na-glass ceramics, on the other hand, there was no positive relation for Li-glass ceramics, indicating that the ion conductive mechanism cannot be explained by the lattice parameter of NASICON crystalline phase alone. The Debye–Waller factors related to the oxygen surrounding the Zr-ion for the Li-glass ceramics were higher than those for the Na-glass ceramics. The static disorder around Zr-ion may cause more weakly bonding between the Li ions and surrounding atoms, resulting in the improvement of ionic conductivity.
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