Despite outstanding electromechanical properties are achieved in KNN-based ceramics, unstable reproducibility of piezoelectric properties remains a challenge to industrial production, owing to a lack of in-depth understanding of grain growth behavior and chemical homogenization throughout the overall solid-state synthesis process. Herein, a significant chemical heterogeneity behavior was found in calcined 0.957K0.48Na0.52Nb0.96Sb0.04O3-0.04Bi0.5Na0.5ZrO3-0.003CaZrO3 powders owing to non-uniform diffusion and competitive chemical reaction among multicomponent reactants. The chemical heterogeneity is significantly alleviated by modulating calcination temperatures and ball-milling the calcined powders. Furthermore, it was demonstrated that the heterogeneous calcined powder with different particle size distribution played a significant role in grain growth behavior and chemical homogenization of bulk ceramics. Finally, we obtained uniform grain size distribution and preferable chemical homogeneity in ceramics with the calcination of 900 °C and undergone twice ball milling, which exhibited superior piezoelectric properties (d33 = 368 pC/N, kp = 0.52). This work provides an effective paradigm to ameliorate the inferior reproducibility of KNN-based ceramics by effectively regulating the processing condition during solid-state synthesis.
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