Realizing Outstanding Energy Storage Performance in KBT‐Based Lead‐Free Ceramics via Suppressing Space Charge Accumulation

Abstract The great potential of K_1/2Bi_1/2TiO₃ (KBT) for dielectric energy storage ceramics is impeded by its low dielectric breakdown strength, thereby limiting its utilization of high polarization. This study develops a novel composition, 0.83KBT‐0.095Na_1/2Bi_1/2ZrO₃‐0.075 Bi_0.85Nd_0.15FeO₃ (KNBNTF) ceramics, demonstrating outstanding energy storage performance under high electric fields up to 425 kV cm⁻¹: a remarkable recoverable energy density of 7.03 J cm⁻³, and a high efficiency of 86.0%. The analysis reveals that the superior dielectric breakdown resistance arises from effective mitigation of space charge accumulation at the interface, influenced by differential dielectric and conductance behaviors between grains and grain boundaries. Electric impedance spectra confirm the significant suppression of space charge accumulation in KNBNTF, attributable to the co‐introduction of Na_1/2Bi_1/2ZrO₃ and Bi_0.85Nd_0.15FeO₃. Phase‐field simulations reveal the emergence of a trans‐granular breakdown mode in KNBNTF resulting from the mitigated interfacial polarization, impeding breakdown propagation and increasing dielectric breakdown resistance. Furthermore, KNBNTF exhibits a complex local polarization and enhances the relaxor features, facilitating high field‐induced polarization and establishing favorable conditions for exceptional energy storage performance. Therefore, the proposed strategy is a promising design pathway for tailoring dielectric ceramics in energy storage applications.