Achieving Ultrahigh Electrocaloric Response in (Bi0.5Na0.5)TiO3-Based Ceramics through B-Site Defect Engineering

Lead-free electrocaloric (EC) ferroelectrics are considered ideal for the next generation of environmentally friendly solid-state refrigeration materials. However, their inferior performance compared to lead-based materials significantly restricts their potential application. According to phase-field simulations, it is predicted that the pinning effect of a moderate number of defects can effectively enhance the reversible polarization response associated with the entropy change. Herein, sodium–bismuth titanate (BNT) ceramics with high spontaneous polarization are selected to construct B-site defects by introducing Li+ and Nb5+. Under an electric field of 6 kV mm–1, ultrahigh EC temperature changes of ΔTpos = 1.77 and ΔTneg = 1.49 K are achieved at 65 °C by direct measurement (ΔTneg > 1 K over 55–120 °C). Furthermore, ΔTneg remains above 0.70 K in the temperature range from 25 to 130 °C, exhibiting immense potential for practical applications. This study offers a promising direction for optimizing the EC response in defect systems.