Superior Capacitive Energy Storage of BaTiO3‐Based Polymorphic Relaxor Ferroelectrics Engineered by Mesoscopically Chemical Homogeneity

Abstract Relaxor ferroelectrics exhibit giant potentials in capacitive energy storage, however, the scales of polar nanoregions determine the critical field values where the polarization saturation occurs. In this work, a mesoscopic structure engineered ergodic relaxor state is realized by adjusting submicron‐grain scaled chemical homogenity, exhibiting polymorphic polar nanoregions of various scales in different grains. This produces a relatively continuous polarization switching with increasing the applied electric field from diverse grains, thus resulting in a linear‐like polarization response feature. As a result, both a giant energy density ( W rec ) ≈15.4 J cm −3 and a field‐insensitive ultrahigh efficiency ( η ) ≈93.2% are simultaneously achieved at 78 kV mm −1 in (Ba, Ca)(Ti, Zr)O 3 ‐(Bi 0.5 Na 0.5 )SnO 3 lead‐free ceramics. Moreover, both the mesoscopic structure heterogeneity and complex high internal stresses in ultrafine grains decrease the temperature sensitivity of the nanodomain structural features. Together with the suppressed high‐temperature defect motion from high ceramic density and submicron grain size, a record‐high temperature stability with W rec = 10.4±5% J cm −3 and η = 96±3% is obtained at 65 kV mm −1 and 0–250 °C, demonstrating great application potential of the studied ceramic in high‐temperature energy storage capacitors. The proposed strategy in this work greatly expands the design mentality for next‐generation high‐performance energy‐storage dielectrics.