In this letter, we use transmission electron microscopy to study the microstructure feature of recently reported Pb-free piezoceramic Ba(Zr_0.2Ti_0.8)O₃-x(Ba_0.7Ca_0.3)TiO₃ across its piezoelectricity-optimal morphotropic phase boundary (MPB) by varying composition and temperature, respectively. The domain structure evolutions during such processes show that in MPB regime, the domains become miniaturized down to nanometer size with a domain hierarchy, which coincides with the d₃₃-maximum region. Further convergent beam electron diffraction measurement shows that rhombohedral and tetragonal crystal symmetries coexist among the miniaturized domains. Strong piezoelectricity reported in such a system is due to easy polarization rotation between the coexisting nano-scale tetragonal and rhombohedral domains.

A pivotal obstacle of obtaining dielectric ceramics with large recoverable energy density (W_rec) and ultrahigh energy efficiency (η) desperately needs to be overcome for the development of advanced energy storage devices for high pulsed power systems, especially via an environment-friendly lead-free method. Here we report a series of lead-free dielectric bulk ceramics for high-temperature energy storage capacitors with near-zero energy loss. Confirmed by aberration-corrected scanning transmission electron microscopy and phase-field simulation, a judiciously designed heterostructure in which rhombohedral and tetragonal polar nanoregions are embedded in a cubic paraelectric matrix was constructed. The combination of the increased breakdown strength and the minimized polarization hysteresis, respectively, based on the heterostructure design and repeated rolling process, contributes to a large W_rec of 10.28 J cm⁻³ and a record-high η of 97.11%, superior to the reported lead-free bulk ceramics. Based on such structure-induced advantages, the wide-temperature stability (25–200 °C) and high performance (W_rec ∼ 6.35 ± 9.1% J cm⁻³, η ∼ 94.82% ± 3.4%) of the dielectric ceramics broaden their application in high temperature energy storage systems. This work conspicuously contributes to the development of the next generation high-temperature capacitors and suggests a new paradigm that may stimulate the development of higher-performance energy storage dielectrics.

Dielectric ceramic capacitors with ultrahigh power densities are fundamental to modern electrical devices. Nonetheless, the poor energy density confined to the low breakdown strength is a long-standing bottleneck in developing desirable dielectric materials for practical applications. In this instance, we present a high-entropy tungsten bronze-type relaxor ferroelectric achieved through an equimolar-ratio element design, which realizes a giant recoverable energy density of 11.0 J·cm⁻³ and a high efficiency of 81.9%. Moreover, the atomic-scale microstructural study confirms that the excellent comprehensive energy storage performance is attributed to the increased atomic-scale compositional heterogeneity from high configuration entropy, which modulates the relaxor features as well as induces lattice distortion, resulting in reduced polarization hysteresis and enhanced breakdown endurance. This study provides evidence that developing high-entropy relaxor ferroelectric material via equimolar-ratio element design is an effective strategy for achieving ultrahigh energy storage characteristics. Our results also uncover the immense potential of tetragonal tungsten bronze-type materials for advanced energy storage applications.