Lead‐free (Na0.53K0.45Li0.02)(Nb0.8Ta0.2)O3 (NKLNT) was prepared using a conventional cold‐pressing method. A commercial piezoresponse force microscope (PFM) was applied to observe the domain structures of NKLNT ceramics. The typical configuration of the ferroelectric domain was analyzed in abnormal grains with grain sizes that exceeded 40 μm, where tetragonal 90° domains are predominant. The local piezoresponse hysteresis loops were characterized and studied as a function of the domain width (dw) in the range 300–1000 nm. It was found that the amplitude signals increased and the coercive field reduced significantly with a decrease in the domain size. Finally, the local longitudinal piezoelectric coefficient (d33) increased as the domain size decreased.
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