High‐Entropy Doping in PZS‐Based Antiferroelectric Ceramics: Enhancing Low Electric‐Field Energy Storage Performance

Abstract

Achieving high recoverable energy storage density (Wrec) and efficiency in dielectric energy storage ceramics under low electric fields is essential to meet the stringent requirements of specific application scenarios concerning integration, safety, and cost; however, most high‐performance dielectric ceramics depend on high electric fields. To address this challenge, the primary strategy involves enhancing polarization differences and achieving delayed hysteresis loops, positioning antiferroelectric (AFE) ceramics as highly promising candidates. In this study, a high‐entropy doping approach is used to systematically regulate the crystal structure, microstructure, and polarization behavior of Pb(Zr, Sn)O3 (PZS)‐based AFE ceramics, while the configurational entropy of the overall compositions remains within the medium‐entropy range. Specifically, the incorporation of high‐entropy (Bi0.2La0.2Na0.2Li0.2Ca0.2)TiO3 dopant suppresses domain growth and weakens long‐range ordered polarization, effectively reducing hysteresis loss and enhancing dielectric reliability. The lattice distortions in the tetragonal phase, together with the stabilized relaxor‐like behavior, synergistically modulate the hysteresis loops. Concurrently, the maximum polarization remains high while maintaining a complete AFE‐to‐ferroelectric phase transition, benefiting from the abnormal grain growth, electrical homogeneity, and overall reduced impedance. The optimal composition achieves a remarkable comprehensive performance of high Wrec and efficiency under a relatively low electric field, along with rapid discharge capability and excellent power density. These findings demonstrate an effective route to overcoming the intrinsic trade‐off between high‐field dependence and Wrec through high‐entropy‐doping driven structural engineering in lead‐based AFE ceramics, thereby maximizing utility within a suitable voltage window for the design of high‐power, high‐reliability dielectric energy‐storage capacitors.