Enhanced relaxor behavior and high energy storage efficiency in niobium substituted (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ ceramics

Abstract The microstructure, dielectric properties, relaxor behavior, and energy storage efficiency of un-substituted and niobium (Nb) substituted (Ba_0.85 Ca_0.15)(Zr_0.1 Ti_0.9) _1-x Nb_xO₃ (for x = 0, 0.02 and 0.05) samples prepared by the solid-state reaction method has been studied in detail. All the samples exhibited perovskite structure with no trace of impurity. Composition-dependent phase transition was also observed on the addition of Niobium. At room temperature, the co-existence of rhombohedral and tetragonal phases is observed in the unsubstituted samples. As the composition changes from x = 0.02 to x = 0.05, a structural change from tetragonal to cubic is observed. A remarkable reduction in grain size, from 90 μm (for x = 0) to 1.21 μm for (x = 0.05), is observed with the addition of Niobium. This result suggests that Niobium acts as a grain growth inhibiter in barium calcium zirconium titanate (BCZT) ceramics. The effect of Niobium on transition temperature is studied from the temperature-dependent dielectric permittivity graph. It was clear that the transition temperature shifted to a lower temperature region, and for x = 0.05, at a very low temperature (−23 °C/250 K) the tetragonal to cubic transition was observed. At x = 0.05, the temperature-dependent dielectric permittivity showed a broadened curve, indicating a diffuse phase transition. The diffuse phase transition in Nb substituted samples is explained by Uchino and Nomura modified Curie Weiss law. Moreover, the observations on temperature-dependent dielectric permittivity measurements at various frequencies suggest that the substitution of Nb⁵⁺ induces relaxor behavior. The energy storage efficiency of unsubstituted and Nb substituted samples was calculated from the polarization versus electric field graph. A high storage efficiency of 84% was obtained for the Nb substituted sample (x = 0.05) at 12 kV cm⁻¹. Enhanced relaxor behavior and increased storage efficiency were observed in (Ba_0.85 Ca_0.15)(Zr_0.1 Ti_0.9) _1-x Nb_xO₃ at x = 0.05. Thus we suggest that these are promising materials for energy storage applications.