Relaxor ferroelectric transition and energy storage enhancement in BaTiO₃ ceramics via high-energy ball milling

This work demonstrates a simple, cost-effective high-energy ball milling route to induce relaxor ferroelectricity in BaTiO₃ (BTO) ceramics for energy storage. Sintered pellets, prepared from both un-milled and milled BTO powders, were characterized by XRD, dielectric spectroscopy, and P–E measurements. X-ray diffraction confirms retention of the tetragonal P4mm phase, with milled pellets showing slight unit‐cell contraction due to milling‐induced structural distortions. Dielectric spectra reveal a shift from a sharp Curie peak (~120 °C) in un-milled pellets to a broad, diffuse transition (60–180 °C) in milled pellets, indicating disrupted long‐range order and the emergence of polar nanoregions (PNRs). Polarization–electric field loops show conventional ferroelectric behavior in unmilled samples (Pᵣ = 10.54 μC/cm², Ec = 16.70 kV/cm), whereas milled pellets exhibit slim hysteresis with reduced Pᵣ (0.94 μC/cm²) and Ec (4.51 kV/cm), reflecting relaxor‐like dynamics. Recoverable energy density (Wₑc) increases from 0.22 to 0.31 J/cm³ and energy efficiency (η) rises from 15% to 85% after milling. These findings underscore high‐energy ball milling as an effective strategy to tailor dielectric properties in conventional ferroelectrics for advanced capacitor applications.