Modifying the high‐temperature dielectric properties of PLZT antiferroelectric ceramics by donor‒acceptor codoping

(Pb,La)(Zr,Ti)O3 antiferroelectric (AFE) ceramics have attracted considerable interest due to their high‐energy storage density and numerous field‐induced phase transitions. However, the positional equilibrium of the A‐site and B‐site is typically maintained without considering that heterovalent doping of La3+ can induce defects within the material, leading to high‐temperature leakage conduction. In this work, we introduced the acceptor ion Na+ at the A‐site simultaneously and designed Pb0.9175–0.5xLa0.055NaxZr0.975Ti0.025O3 (x = 0.01, 0.03, 0.055, 0.07, 0.10) AFE ceramics. The dielectric properties of these ceramics exhibited a consistent pattern of improvement followed by deterioration as the content of Na+ increased. Notably, when x = 0.055 (Na5.5), the AFE ceramic demonstrated superior high‐temperature frequency stability with negligible leakage conduction. Impedance spectroscopy analysis suggested that Na5.5 displays the greatest resistance and highest Edc. Concurrently, the thermally stimulated depolarization current indicates that Na5.5 possesses the lowest defect concentration and the largest Ea. This can be attributed to the internal generation of defect dipole clusters (), which effectively restrict the movement of charged defects. These findings suggest that Na5.5 holds significant potential for application and offer insights into the understanding of internal defects in lead‐based AFE materials.