In the present era of advanced technology, the surge for suitable multifunctional materials capable of operating above 300 °C has increased for the utilization of high-temperature piezoelectric devices. For this purpose, a pseudo-tetragonal phased CaBi4Ti3.98 (Nb0.5Fe0.5)0.02O15:xwt%MnO2 (CBTNF:xMn), with x = 0–0.20, ceramic system has been engineered for the investigation of structural, ferroelectric, dielectric and high-temperature-dependent piezoelectric properties. XRD analysis confirms that low-content Mn-ion insertion at the lattice sites of CBTNF does not distort the pseudo-tetragonal phase lattice of CBTNF:xMn ceramics, but enhances the functional behavior of the ceramic system, specifically at x = 0.15 wt%Mn. Compared to pure CBT and CBTNF ceramics, CBTNF:0.15Mn has demonstrated a highly dense relative density (~96%), a saturated polarization (PS) of 15.89 µC/cm2, a storage energy density (WST) of ~1.82 J/cm3, an energy-conversion efficiency (ƞ) of ~51% and an upgraded piezoelectric behavior (d33) of 27.1 pC/N at room temperature. Sharp temperature-dependent dielectric constant (εr) peaks display the solid ferroelectric behavior of the CBTNF:0.15Mn sample with a Curie temperature (TC) of 766 °C. The thermally stable piezoelectric performance of the CBTNF:0.15Mn ceramic was observed at 600 °C, with just a 0.8% d33 loss (25 pC/N). The achieved results signify that multi-valence Mn ions have effectively intercalated at the lattice sites of the pseudo-tetragonal phased CBTNF counterpart and enhanced the multifunctional properties of the ceramic system, proving it to be a durable contender for utilization in energy-storage applications and stable high-temperature piezoelectric applications.
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