Re-entrant relaxor ferroelectric behaviour is identified in BiFeO₃–BaTiO₃ ceramics, yielding anomalous thermal variations in structural distortion and functional properties.

BiFeO₃–BaTiO₃ (BF–BT) ceramics exhibit great potential for diverse applications in high temperature piezoelectric transducers, temperature-stable dielectrics and pulsed-power capacitors. Further optimization of functional properties for different types of applications can be achieved by modification of processing parameters or chemical composition. In the present work, the influence of pentavalent niobium substitution for trivalent ferric ions on the structure, microstructure and dielectric properties of 0.7BF–0.3BT ceramics was investigated systematically. Doping with niobium led to incremental reductions in grain size (from 7.0 to 1.3 µm) and suppression of long-range ferroelectric ordering. It was found that core-shell type microstructural features became more prominent as the Nb concentration increased, which were correlated with the formation of distinct peaks in the dielectric permittivity–temperature relationship, at ~470 and 600 °C, which were attributed to the BT-rich shell and BF-rich core regions, respectively. Nb-doping of BF–BT ceramics yielded reduced electronic conductivity and dielectric loss, improved electrical breakdown strength and enhanced dielectric energy storage characteristics. These effects are attributed to the charge compensation of pentavalent Nb donor defects by bismuth vacancies, which suppresses the formation of oxygen vacancies and the associated electron hole conduction mechanism. The relatively high recoverable energy density (W_rec = 2.01 J cm⁻³) and energy storage efficiency (η = 68%) of the 0.7BiFeO₃–0.3BaTiO₃ binary system were achieved at 75 °C under an electric field of 15 kV mm⁻¹. This material demonstrates the greatest potential for applications in energy storage capacitors and temperature-stable dielectrics.

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 (P_s) and remnant polarization (P_r) 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.