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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 (UV‒Vis) spectroscopy reveal a decrease in the oxygen vacancy concentration and an increase in the bandgap for higher CaZrO3 doping levels. These changes synergistically enhance the maximum applied electric field, helping to achieve a high-performance ECE near room temperature. This research presents a straightforward and effective approach for achieving high-performance ECEs in BaTiO3 lead-free ceramics, offering promising prospects for application in next-generation solid-state refrigeration technologies.
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