Tunable electrocaloric and energy storage behavior in the Ce,Mn hybrid doped BaTiO3 ceramics

The electrocaloric effect and energy storage property are tuned in the Ba_1-xCe_xTi_0.99Mn_0.01O₃ ceramics prepared by the solid state reaction method. The ceramics with lower Ce content (x?=?0.005, 0.015) show a better ΔT and ΔT/ΔE response. The ceramics with higher Ce content (x?=?0.030, 0.040, 0.045) represent the broader ΔT peaks (50?K–60?K), and the higher energy storage density and efficiency. The largest electrocaloric response (ΔT_max?=?1.22?K, ΔT/ΔE?=?0.41?K mm/kV) is found in the Ba_0.995Ce_0.005Ti_0.99Mn_0.01O₃ ceramics, which is comparable or even higher than that of the most isovalent substituting BaTiO₃-based ceramics reported before. The maximum energy storage density 0.11?J/cm³ (E?=?30?kV/cm) is obtained for the Ba_0.970Ce_0.030Ti_0.99Mn_0.01O₃ ceramics, with high efficiency of 65–88% over a wide temperature range of 72?K. This work may open more opportunities to design high electrocalaric and energy storage performance lead-free systems from the viewpoint of the heterovalent and size mismatch substitution.