Enhanced electrocaloric effect over a broad temperature range in lead‐free Na0.5Bi0.5TiO3‐based relaxor ferroelectrics via doping with Bi(Mg0.5Zr0.5)O3

Abstract With an increasing demand for environmentally friendly refrigeration, the solid‐state refrigeration based on the electrocaloric effect (ECE) has been drawn extensive attention. It is a challenge to maintain a large adiabatic temperature change (∆T) over a broad temperature span. Herein, the authors designed and synthesised (0.74‐x) Na0.5Bi0.5TiO3‐0.06BaTiO3‐0.2SrTiO3‐xBi(Mg0.5Zr0.5)O3 (abbreviated as NBT‐xBMZ) (x = 0, 0.02, 0.04, 0.06 and 0.08) lead‐free relaxor ferroelectrics. Their microstructures, dielectric properties, ferroelectric properties, ECEs and the structure‐property relationships were investigated. Via doping with BMZ, an enhanced relaxor feature and a wider temperature range where multi‐phases coexist were achieved. The relaxor ferroelectric characteristics were illustrated using the Vogel‐Fulcher relation. The indirectly calculated ECE results showed that the optimal ΔT of 1.11 K was obtained for the x = 0.02 sample at 90°C and 70 kV/cm over a wide Tspan of 120°C, providing a potential ECE material. The direct ECE results procured using thermocouple indicated that the maximal ∆T of 2.14 K and ∆T/∆E of 0.31 K m/MV were achieved in the same sample at 70°C and 7 MV/m and the variation trend of ECE results was consistent with the indirect results. Moreover, the multi‐phases coexistent strategy can be extended to other materials system to generate a large ΔT over a wide temperature range.