Excellent Energy Storage and Charge–Discharge Performance in (Pb<sub>1–<i>x</i></sub>Ca<sub><i>x</i></sub>)(Zr<sub>0.55</sub>Sn<sub>0.45</sub>)O<sub>3</sub> Antiferroelectric Ceramics
Chao Yu, Shibin Wang, Xuling Yan, Weiqiu Li, Yuliang Yu, Xiaobo Zhao, Yingbang Yao, Tao Tao, Bo Liang, Weiping Gong, Sheng‐Guo Lu
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– x Ca x ) (Zr 0.55 Sn 0.45 )O 3 (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 Ca 2+ 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 0.98 Ca 0.02 ) (Zr 0.55 Sn 0.45 )O 3 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/cm 3 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/cm 3 and a discharged energy density ( W dis ) of 6.24 J/cm 3 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.