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The electrocaloric effect (ECE) in lead-free (Bi0.5Na0.5)TiO3-SrTiO3 (BNT-ST) ceramics was investigated by direct and indirect measurements. Polarization-electric field hysteresis loops of the BNT-ST ceramics changed from well-saturated shapes at room temperature to constricted shapes around the depolarization temperature due to an electric field-induced phase transition. A large adiabatic temperature change due to ECE (ΔTEC) was obtained around the phase transition temperature (TFR) by indirect measurements, which was confirmed by direct measurements. The 0.85BNT-0.15ST sample showed a large negative ΔTEC in the indirect measurements below TFR where the polarization increases, while the directly measured ΔTEC displayed positive values. It suggests that the indirect method using the Maxwell relation is not valid in the temperature range where the polarization increases with temperature. The X-ray diffraction structural refinements showed that the poled 0.85BNT-0.15ST sample has mixed phases of a rhombohedral R3C and a tetragonal P4bm in the temperature range where the polarization increases below TFR.

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