Simultaneous achievement of large electrocaloric effect and ultra-wide operating temperature range in BaTiO₃-based lead-free ceramic

The electrocaloric effect (ECE), known for its environmentally friendly characteristics, holds significant promise for advancing next-generation solid-state refrigeration technologies. Achieving a large ECE along with a wide working temperature range near room temperature remains a key developmental goal. In this study, we successfully obtained a substantial ECE of 1.78 K and an extensive working temperature range of 103 K (ΔT > 1.52 K) near room temperature in CaZrO₃ modified BaTiO₃ lead-free ferroelectric ceramics. Furthermore, this achievement was verified using direct methods. The piezoresponse force microscopy (PFM) results suggest that the broad temperature range is attributed to the formation of ferroelectric microdomains and polar nanoregions (PNRs). Furthermore, X-ray photoelectron spectroscopy (XPS) and ultraviolet-visible spectroscopy (UV-vis) reveal a decrease in oxygen vacancy concentration and an increase in bandgap for higher CaZrO₃ doping levels. These changes synergistically enhance the maximum applied electric field, helping to achieve high-performance ECE near room temperature. The research presents a straightforward and effective approach in achieving high-performance ECE in BaTiO₃ lead-free ceramics, offering promising prospects for application in next-generation solid-state refrigeration technologies.