BiFeO3–based ceramics possess an advantage over large spontaneous polarization and high Curie temperature, and are thus widely explored in the field of high–temperature lead–free piezoelectrics and actuators. However, poor piezoelectricity/resistivity and thermal stability of electrostrain make them less competitive. To address this problem, (1 − x) (0.65BiFeO3–0.35BaTiO3)–xLa0.5Na0.5TiO3 (BF–BT–xLNT) systems are designed in this work. It is found that piezoelectricity is significantly improved with LNT addition, which is contributed by the phase boundary effect of rhombohedral and pseudocubic phase coexistence. The small–signal and large–signal piezoelectric coefficient (d33 and d33*) peaks at x = 0.02 with 97 pC/N and 303 pm/V, respectively. The relaxor property and resistivity are enhanced as well. This is verified by Rietveld refinement, dielectric/impedance spectroscopy and piezoelectric force microscopy (PFM) technique. Interestingly, a good thermal stability of electrostrain is obtained at x = 0.04 composition with fluctuation η = 31% (Smax'−SRTSRT×100%), in a wide temperature range of 25–180 °C, which is considered as a compromise of negative temperature dependent electrostrain for relaxors and the positive one for ferroelectric matrix. This work provides an implication for designing high–temperature piezoelectrics and stable electrostrain materials.
