High electrocaloric effect in barium titanate-sodium niobate ceramics with core-shell grain assembly

Electrocaloric effect (ECE) is promising in realizing solid-state cooling as an alternative to the conventional refrigeration with environmentally harmful coolant and low efficiency. High ECE in lead-free ferroelectric ceramics is highly desirable for the EC cooling. In this work, different from the researches that tune the ECE by conventional compositional design or external stress engineering, we fabricated the (1-x)BaTiO3-xNaNbO3 (BTO-xNN) lead-free ceramics with a core-shell grain structure arising from the inhomogeneous stoichiometry of element distribution, leading to the internal compressing stress in the grains. It is interesting that the phase transition behavior, including the phase transition temperature and the diffusion property, is regulated by the core-shell grain structure induced internal stress, which can be capitalized on for the favorable ECE. Cooperated with 0.02 NN, a high ECE, e.g. adiabatic temperature change (ΔT) of 3.6 K and isothermal entropy change (ΔS) of 4.5 J kg−1 K−1, is attained in the BTO ceramic. As the internal stress further increases with more NN, the BTO-0.06NN exhibits an extremely stable ECE with a variety rate below ±4% in a wide temperature range from 300 K to 360 K. This work provides a novel approach to explore pronounced ECE in lead-free ferroelectrics for eco-friendly refrigeration.