Enhanced electrocaloric effect, energy storage density and pyroelectric response from a domain-engineered lead-free BaTi0.91Sn0.08Zr0.01O3 ferroelectric ceramic

Abstract

A BaTi_0.91Sn_0.08Zr_0.01O₃ (BTSZ) ceramic was prepared by a conventional solid-state reaction method. Its structural, dielectric, ferroelectric, and pyroelectric properties were carefully studied. The Rietveld refinement was used to characterize the structural proprieties of the synthesized ceramic. The microstructure was observed by scanning electron microscopy. Phase transitions observed in the temperature dependent dielectric permittivity (ε_r–T and tan δ–T) showed a transition close to room temperature, resulting in improved piezoelectric, pyroelectric and electrocaloric performance. In addition, it was found that an electric field poling process changed the character of ε_r–T and tan δ–T plots. Resonance modes in the polarized state, where maximum power transmission was achieved, were observed in the impedance spectrum. The extra-slim hysteresis loops revealed a relatively low coercive field and hysteresis loss related to the diffuse phase transition, which can significantly improve energy storage efficiency up to 75% at 100 °C. To characterize the electrocaloric effect (ECE), indirect and direct methods based on the thermodynamic approach were used. Both methods results showed good consistency and revealed a large ECE peak evolving along the phase diagram. Furthermore, pyroelectric figures of merit (FOMs) for voltage responsivity (F_v), current responsivity (F_i), energy harvesting (F_E), new energy harvesting and detectivity (F_d) were calculated. Finally, thermal energy harvesting (N_D) was determined by using the Olsen cycle. The obtained maximum N_D was 233.7 kJ m⁻³ when the Olsen cycle operated at 25–100 °C and 0–30 kV cm⁻¹. This study introduces not only a technique to produce a high performance ceramic for refrigeration devices, but also broadens the range of applications for BT-based lead-free ferroelectrics beyond actuators, sensors, and energy harvesting to solid-state cooling.