Improvement of Electro-Caloric Effect and Energy Storage Density in BaTiO-Bi(Zn, Ti)O Ceramics Prepared with BaTiO Nano-Powder.

BaTiO-Bi(Zn,Ti)O (BT-BZT) ceramics have been used as capacitors due to their large dielectric permittivity and excellent temperature stability and are good candidates for lead-free materials for electrocaloric and energy storage devices. However, BT-BZT ceramics often suffer from inferior properties and poor reproducibility due to heterogeneous compositional distribution after calcination and sintering. In this work, (1-)BT-BZT ceramics ( = 0~0.2) were fabricated with nano-sized BaTiO raw materials (nano-BT) by a solid-state reaction method to enhance the chemical homogeneity. The (1-)BT-BZT ceramics prepared from the nano-BT showed larger densities and more uniform microstructures at the lower calcination and sintering temperatures than the samples prepared from more frequently used micrometer-sized raw materials BaCO, TiO, BiO, and ZnO. The (1-)BT-BZT ceramic prepared from the nano-BT displayed a phase transition from a tetragonal ferroelectric to a pseudo-cubic relaxor in a narrower composition range than the sample prepared from micro-sized raw materials. Larger adiabatic temperature changes due to the electro-caloric effect (ΔT) and recoverable energy storage density () were observed in the samples prepared from the nano-BT due to the higher breakdown electric fields, the larger densities, and uniform microstructures. The 0.95BT-0.05BZT sample showed the largest ΔTECE of 1.59 K at 80 °C under an electric field of 16 kV/mm. The 0.82BT-0.18BZT sample displayed a of 1.45 J/cm, which is much larger than the previously reported value of 0.81 J/cm in BT-BZT ceramics. The nano-BT starting material produced homogeneous BT-BZT ceramics with enhanced ECE and energy storage properties and is expected to manufacture other homogeneous solid solutions of BaTiO and Bi-based perovskite with high performance.