Excellent Energy Storage and Charge–Discharge Performance in (Pb1–xCax)(Zr0.55Sn0.45)O3 Antiferroelectric Ceramics

Abstract

Lead-based antiferroelectric (AFE) ceramics have the advantages of high power density, fast charge and discharge speed, and the electric-field-induced AFE-FE phase transition, making them one of the potential dielectric energy storage materials. However, the energy storage density still needs to be improved. In this work, (Pb_1–xCa_x) (Zr_0.55Sn_0.45)O₃ (PCZS, x = 0.01, 0.02, 0.03 and 0.04) antiferroelectric ceramics were successfully prepared using the solid-state reaction and two-step sintering methods. The results showed that as the Ca²⁺ content increased, the average grain size decreased from 1.38 ± 0.42 to 1.06 ± 0.35 μm and the dielectric breakdown strength increased from 270 to 325 kV/cm for ceramics with 80 μm in thickness. Two kinds of superlattice structures (F-point with 1/2{ooo} patterns and incommensurate modulation structure (IMS) pattern with 1/n{110} patterns) were observed, indicating the typical octahedral tilting-related AFE structure. The (Pb_0.98Ca_0.02) (Zr_0.55Sn_0.45)O₃ bulk ceramics, due to the refined polarization–electric field hysteresis loop of the IMS, achieved a maximum recoverable energy storage density (W_rec) of 6.61 J/cm³ with an efficiency (η) of 84.01%. In the circuit of charge–discharge to a load, an ultrahigh power density (P_D) of 276.67 MW/cm³ and a discharged energy density (W_dis) of 6.24 J/cm³ were obtained in PCZS2 bulk ceramics at 290 kV/cm. The high W_rec and W_dis indicate that PCZS ceramics offer potential applications in the field of pulse-power electric devices.