Fluoride solid electrolytes containing rare earth elements
来源期刊：JOURNAL OF RARE EARTHS2008年第2期
论文作者：Ivan Furár Pavel P. Fedorov Viera Trnovcová
Key words：rare earth containing fluorides; superionic conductivity; defects; conduction mechanisms; clustering; single crystals; composites;
Abstract: Relations between the structure, ionic conductivity and dielectric properties of fluoride systems of different structures containing rare earth elements were presented. Superionic conductivities, by fluoride ions, of fluorite-structured (MF2-REF3, M=Ba, Pb, RE=La-Lu, Sc, Y), orthorhombic (REF3, RE=Tb-Er,Y), tysonite-structured (REF3-MF2, RE=La-Nd, M=Sr), monoclinic (BaRE2F8, RE=Ho-Yb, Y) fluoride single crystals and eutectic composites (LiF-REF3, RE=La-Gd,Y) were compared. Anisotropy of electrical properties of crystals with a lower symmetry was explained by modeling optimum ionic paths. For explanation of concentration dependences of fast ionic conductivity, models of aggregation of defects into clusters were proposed. In fluorite-structured crystals, the highest ionic conductivity was found for PbF2: 7 mol% ScF3 (at 500 K, σ500=0.13 S/cm). In tysonite-structured crystals, the highest ionic conductivity was found for LaF3: 3 mol% SrF2 (σ500=2.4×10-2 S/cm). Different types of coordination polyhedrons and their different linking in orthorhombic and tysonite structure explained large differences between conductivities in both structures. Eutectic systems, prepared as directionally solidified composites, enabled to study some orthorhombic fluoride phases (GdF3, SmF3), which cannot be prepared as single crystals. An influence of the orthorhombic-tysonite phase transition on the ionic conductivity was shown.
Ivan Furár1，Pavel P. Fedorov2，Viera Trnovcová1
(1.Department of Physics, Faculty of Materials Science and Technology, Slovak University of Technology, SK-91724 Trnava, Slovakia;
2.Institute of General Physics, Russian Academy of Sciences, Moscow, Russia)
Abstract:Relations between the structure, ionic conductivity and dielectric properties of fluoride systems of different structures containing rare earth elements were presented. Superionic conductivities, by fluoride ions, of fluorite-structured (MF2-REF3, M=Ba, Pb, RE=La-Lu, Sc, Y), orthorhombic (REF3, RE=Tb-Er,Y), tysonite-structured (REF3-MF2, RE=La-Nd, M=Sr), monoclinic (BaRE2F8, RE=Ho-Yb, Y) fluoride single crystals and eutectic composites (LiF-REF3, RE=La-Gd,Y) were compared. Anisotropy of electrical properties of crystals with a lower symmetry was explained by modeling optimum ionic paths. For explanation of concentration dependences of fast ionic conductivity, models of aggregation of defects into clusters were proposed. In fluorite-structured crystals, the highest ionic conductivity was found for PbF2: 7 mol% ScF3 (at 500 K, σ500=0.13 S/cm). In tysonite-structured crystals, the highest ionic conductivity was found for LaF3: 3 mol% SrF2 (σ500=2.4×10-2 S/cm). Different types of coordination polyhedrons and their different linking in orthorhombic and tysonite structure explained large differences between conductivities in both structures. Eutectic systems, prepared as directionally solidified composites, enabled to study some orthorhombic fluoride phases (GdF3, SmF3), which cannot be prepared as single crystals. An influence of the orthorhombic-tysonite phase transition on the ionic conductivity was shown.
Key words:rare earth containing fluorides; superionic conductivity; defects; conduction mechanisms; clustering; single crystals; composites;
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