Effect of Bi(Mg0.5Ti0.5)O3 addition on the dielectric and electrocaloric properties of relaxor (Na0.5Bi0.5)TiO3 - BaTiO3 ceramics

The electrocaloric effect (ECE) refers to the isothermal entropy or adiabatic temperature change of polar crystals when an electric field is applied or removed. This effect is a promising approach for the development of compact solid state coolers. Among the promising materials are environmentally friendly lead-free relaxors of the (Na0.5Bi0.5)TiO3 –BaTiO3 (NBT-BT) family showing a large ECE in a wide temperature range. Intriguingly, some groups have reported negative ECE in these materials and attributed this to the antiferroelectric features of NBT. Both relaxor and antiferroelectric properties of NBT can be enhanced by doping, e.g., by adding bismuth magnesium titanate (BMT). In this study, the effect of the incorporation of BMT on the structural, electrical, and electrocaloric properties of lead-free ceramics (1-x)[0.95(Na0.5Bi0.5)TiO3-0.05BaTiO3]-(x)Bi(Mg0.5Ti0.5)O3, where x = 0, 0.1, and 0.2, was investigated. The temperature dependences of the dielectric permittivity exhibit behavior characteristic of relaxors. With increasing BMT content, the maximum polarization value decreases from 23 to 8.5 μC/cm2, and the depolarization temperature shifts from 322 to 254 K, which points out an enhancement in relaxor properties. We have shown that double hysteresis loops observed in the studied materials are not caused by the antiferroelectric nature of the compositions, but by the pinning effect by point defects. Furthermore, the negative ECE estimated from the indirect measurements using Maxwell's relation was not confirmed by the direct measurements using a quasi-adiabatic calorimeter. The interplay between defect dipoles and the role of BMT in stabilization of ergodic relaxor behavior at lower temperatures and electrocaloric effects are discussed. The study also shows that the NBT-5BT-10BMT composition is promising for energy storage applications.