Doping-Induced Relaxor Ferroelectricity and Site Engineering in Ba1–xPr2x/3Ti1–y(Mo1/2Nb1/2)yO3Ceramics for Enhanced Permittivity and Energy Storage Performance

Abstract

In this study, site engineering at the Ba and Ti sites of BaTiO3has been done to develop Ba1–xPr2x/3Ti1–y(Mo1/2Nb1/2)yO3[BTMN] ceramics, with x = 0.003 and y = 0.02, 0.04, 0.06, 0.08, 0.1, to improve permittivity and energy storage performance. The solid-state reaction method was used to synthesize samples. X-ray diffraction analysis revealed a crystallographic phase transition from tetragonal (P4mm) to cubic (Pm-3m) structure with increasing (Mo1/2Nb1/2) concentration. Raman spectroscopy further validates this finding with the disappearance of the characteristic tetragonal peak at 303 cm–1for higher dopant levels (y ≥ 0.06). Grain size displays a nonlinear trend where grain size first increases to 0.49 μm for intermediate compositions and then decreases to 0.25 μm at higher dopant levels. Dielectric characterization revealed that the increased relative permittivity (εr= 2840.46 at 20 Hz) and low dielectric loss (0.0390) have been achieved for the BTMN06 sample, and all other compositions exhibited low dielectric loss (<0.055) in the frequency range 20 Hz to 100 kHz. Permittivity decreased with increasing frequency, which is consistent with Maxwell–Wagner polarization effects. Curie temperature (Tc) shifted downward from 115 °C (BTMN02) to 31 °C (BTMN10), reflecting increased structural disorder induced by doping. Relaxor behavior was quantified by an increasing diffusion parameter (1.28 to 1.95) for permittivity, with enhanced polarization stability and slim P–E hysteresis loops at higher dopant levels. Energy storage characteristics showed superior recoverable energy densities (317.7 mJ/cm3for BTMN08 and 292.2 mJ/cm3for BTMN10 with efficiencies 91 and 92.6% respectively), validating the material’s potential for high-efficiency capacitive energy storage in advanced applications. © 2025 The Authors. Published by American Chemical Society