Phase and defect structures of MnO2‐doped 75BiFeO3–25BaTiO3 ceramics and their effects on electrical properties.

Bismuth ferrite (BiFeO3)‐based high‐temperature piezoelectric ceramics have high Curie temperatures and excellent thermal stability; however, their applications are limited by inadequate piezoelectric performance due to large coercive fields and high leakage conduction. This study investigates the impact of MnO2 doping on the phase transition, defect structure, domain morphology, as well as the dielectric, ferroelectric, and electrical conduction behaviors of 75BiFeO3–25BaTiO3 ceramics sintered under an oxygen atmosphere. A structural transformation from distorted rhombohedral to pseudo‐cubic symmetry was observed with increasing MnO2 content, accompanied by domain fragmentation. MnO2 doping at an appropriate level inhibited defects such as Fe′Fe$\ {\mathrm{F}}{{{\mathrm{e^{\prime}}}}_{{\mathrm{Fe}}}}$ and VO2−⋅⋅$V_{{{{\mathrm{O}}}^{{\mathrm{2}} - }}}^{\centerdot \centerdot }$. Regarding electrical properties, the reduction in rhombohedral distortion and enhancement in the pseudo‐cubic phase after MnO2 doping resulted in decreased remanent polarization and electrostrain, which could potentially hinder piezoelectric response. However, appropriate MnO2 doping effectively reduced leakage conduction, significantly enhancing the poling efficiency of the ceramics. The maximum d33 value of 107 pC/N and kp of 0.36 were achieved at an MnO2 doping content of 0.1 wt.%. Excessive MnO2 addition may generate 2Mn′Ti−VO2−⋅⋅${\mathrm{2M}}{{{\mathrm{n^{\prime}}}}_{{\mathrm{Ti}}}}-V_{{{{\mathrm{O}}}^{{\mathrm{2}} - }}}^{\centerdot \centerdot }$ defect dipoles, as indicated by increased coercive field (Ec) and dielectric loss. The observed increase in high‐temperature resistivity with MnO2 content is primarily attributed to reduced grain size and increased concentration of mobile defects. This study provides valuable insights for further research on the application of 75BiFeO3–25BaTiO3 systems in high‐temperature piezoelectric devices. [ABSTRACT FROM AUTHOR]