Next-generation advanced high/pulsed power capacitors rely heavily on dielectric ceramics with high energy storage performance. However, thus far, the huge challenge of realizing ultrahigh recoverable energy storage density (W_rec) accompanied by ultrahigh efficiency (η) still existed and has become a key bottleneck restricting the development of dielectric materials in cutting-edge energy storage applications. Here, we propose a high-entropy strategy to design “local polymorphic distortion” including rhombohedral-orthorhombic-tetragonal-cubic multiphase nanoclusters and random oxygen octahedral tilt, resulting in ultrasmall polar nanoregions, an enhanced breakdown electric field, and delayed polarization saturation. A giant W_rec ~10.06 J cm⁻³ is realized in lead-free relaxor ferroelectrics, especially with an ultrahigh η ~90.8%, showing breakthrough progress in the comprehensive energy storage performance for lead-free bulk ceramics. This work opens up an effective avenue to design dielectric materials with ultrahigh comprehensive energy storage performance to meet the demanding requirements of advanced energy storage applications.

Advanced lead-free energy storage ceramics play an indispensable role in next-generation pulse power capacitors market. Here, an ultrahigh energy storage density of ~ 13.8 J cm⁻³ and a large efficiency of ~ 82.4% are achieved in high-entropy lead-free relaxor ferroelectrics by increasing configuration entropy, named high-entropy strategy, realizing nearly ten times growth of energy storage density compared with low-entropy material. Evolution of energy storage performance and domain structure with increasing configuration entropy is systematically revealed for the first time. The achievement of excellent energy storage properties should be attributed to the enhanced random field, decreased nanodomain size, strong multiple local distortions, and improved breakdown field. Furthermore, the excellent frequency and fatigue stability as well as charge/discharge properties with superior thermal stability are also realized. The significantly enhanced comprehensive energy storage performance by increasing configuration entropy demonstrates that high entropy is an effective but convenient strategy to design new high-performance dielectrics, promoting the development of advanced capacitors "Image missing".