Field‐Induced Multiscale Polarization Configuration Transitions of Mesentropic Lead‐Free Piezoceramics Achieving Giant Energy Harvesting Performance

Abstract The development of high‐performance (K,Na)NbO₃ (KNN)‐based lead‐free piezoceramics for next‐generation electronic devices is crucial for achieving environmentally sustainable society. However, despite recent improvements in piezoelectric coefficients, correlating their properties to underlying multiscale structures remains a key issue for high‐performance KNN‐based ceramics with complex phase boundaries. Here, this study proposes a medium‐entropy strategy to design “local polymorphic distortion” in conjunction with the construction of uniformly oversize grains in the newly developed KNN solid‐solution, resulting in a novel large‐size hierarchical domain architecture (≈0.7 µm wide). Such a structure not only facilitates polarization rotation but also ensures a large residual polarization, which significantly improves the piezoelectricity (≈3.2 times) and obtains a giant energy harvesting performance (W_out = 2.44 mW, P_D = 35.32 µW mm⁻³, outperforming most lead‐free piezoceramics). This study confirms the coexistence of multiphase through the atomic‐resolution polarization features and analyzes the domain/phase transition mechanisms using in situ electric field structural characterizations, revealing that the electric field induces highly effective multiscale polarization configuration transitions based on T–O–R sequential phase transitions. This study demonstrates a new strategy for designing high‐performance piezoceramics and facilitates the development of lead‐free piezoceramic materials in energy harvesting applications.