Synergistic effects of Zn B-site substitution in lead-free Ba0.95Ca0.05Ti0.92Sn0.08O3 ferroelectric ceramics for enhancing piezoelectric properties in energy harvesting applications

In this study, lead-free (Ba0.95Ca0.05)(Ti0.92Sn0.08)O3 (BCTS) and(Ba0.95Ca0.05)(Ti0.912Sn0.08Zn0.008)O3 (BCTS-Zn) ceramics with large piezoelectric properties were prepared via the conventional solid-state reaction. The effect of Zn B-site substitution on the structural, dielectric, ferroelectric, energy storage, electrocaloric and piezoelectric properties of BCTS ceramics were systematically investigated. X ray diffraction analysis and Raman spectroscopy of BCTS and BCTS-Zn ceramics confirm the formation of pure phase structure with the coexistence of orthorhombic, tetragonal and pseudo cubic phases at room temperature. The in-troduction of Zn into BCTS lattice resulted in a denser microstructure with larger average grain size which contributed in the enhancement of the dielectric constant maximum by-35%. Furthermore, the sub-stitution of Ti4+ with a small amount of Zn2+ (0.008) induced a shift in TR-O, TO-T and TT-C transitions towards higher temperatures in addition to an increase in the diffused phase transition character. Moreover, with Zn substitution, an amelioration in the maximum energy storage efficiency is observed from-83% in BCTS ceramic to-88% in BCTS-Zn ceramic. The electrocaloric properties were investigated using the direct and indirect methods. The highest value of the electrocaloric temperature change Delta T = 0.361 K at 319 K was calculated for BCTS ceramic using Maxwell approach with a relatively low electric field of 17.55 kV/cm. For BCTS-Zn ceramic, the enhancement of the piezoelectric properties (d33 = 420 pC/N, g33 = 23.02 mV/mN, FoM = 9.66 pm2/N) is attributed to the synergistic effect of the (O-PC-T) multiphase coexistence, large average grain size and high density of the ceramic. This study reveals that B site Zn substitution in BCTS lattice is an effective approach to improve the piezoelectric properties of the ceramic for energy harvesting applications. (c) 2023 Elsevier B.V. All rights reserved.