BaTiO
3-based piezoelectric ceramics have attracted considerable attention in recent years due to their tunable phase structures and good piezoelectric properties. In this work, the (1 −
x)BaTiO
3−xCaSnO
3 (0.00 ≤
x ≤ 0.16, abbreviated as BT
−
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BaTiO
3-based piezoelectric ceramics have attracted considerable attention in recent years due to their tunable phase structures and good piezoelectric properties. In this work, the (1 −
x)BaTiO
3−xCaSnO
3 (0.00 ≤
x ≤ 0.16, abbreviated as BT
−xCS) solid solutions, were prepared by traditional solid-state reaction methods. The phase transitions, microstructure, dielectric, piezoelectric, and ferroelectric properties of BT-
xCS have been investigated in detail. The coexistence of rhombohedral, orthorhombic, and tetragonal phases near room temperature, i.e., polymorphic phase transition (PPT), has been confirmed by X-ray diffraction and temperature-dependent dielectric measurements in the compositions range of 0.06 ≤
x ≤ 0.10. The multiphase coexistence near room temperature provides more spontaneous polarization vectors and facilitates the process of polarization rotation and extension by an external electric field, which is conducive to the enhancement of piezoelectric response. Remarkably, the composition of BT-0.08CS exhibits optimized piezoelectric properties with a piezoelectric coefficient
d33 of 620 pC/N, electromechanical coupling factors
kp of 58%,
kt of 40%, and a piezoelectric strain coefficient
d33* of 950 pm/V.
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