Temperature-Dependent Ferroelectric Properties and Aging Behavior of Freeze-Cast Bismuth Ferrite-Barium Titanate Ceramics

Lead-free BiFeO₃–BaTiO₃ (BF-BT) piezoceramics have sparked considerable interest in recent years due to their high piezoelectric performance and high Curie temperature. In this paper, we show how the addition of highly aligned porosity (between 40 and 60 vol %) improves the piezoelectric performance, sensing, and energy harvesting figures of merit in freeze-cast 0.70BiFeO₃–0.30BaTiO₃ piezoceramics compared to conventionally processed, nominally dense samples of the same composition. The dense and porous BF-BT ceramics had similar longitudinal piezoelectric coefficients (d₃₃) immediately after poling, yet the dense samples were observed to age faster than those of porous ceramics. After 24 h, for example, the porous samples had significantly higher d₃₃ values ranging from 112 to 124 pC/N, compared to 85 pC/N for the dense samples. Porous samples exhibited 3 and 5 times higher longitudinal piezoelectric voltage coefficient g₃₃ and energy harvesting figure of merit d₃₃g₃₃ than dense samples due to the unexpected increase in d₃₃ and decrease in relative permittivity with porosity. Spontaneous polarization (Ps) and remnant polarization (Pr) decrease as the porosity content increased from 37 to 59 vol %, as expected due to the lower volume of active material; however, normalized polarization values with respect to porosity level showed a slight increase in the porous materials relative to the dense BF-BT. Furthermore, the porous ceramics showed improved temperature-dependent strain–field response compared to the dense. As a result, these porous materials show excellent potential for use in high temperature sensing and harvesting applications.