Abstract: | In this study, the intermediate rare-earth oxide Gd2O3 (Gd) was substituted in different amounts (x = 0.2–2 mol%) for the formulation of BaTi1-xGdxO3-x/2 (BTGx) dielectric materials. The effect of B-site substitution was confirmed by the additional Raman active A1g octahedral peak at ~835cm-1 strengthened at x ≥ 0.4 mol%. Additionally, properties of 0.9BTG0.007-0.1BA dielectric ceramics were analysed based on the influence of various processing methods as a function of sintering temperature. The focal samples were labelled Method-A (direct-mix) and Method-B (indirect-mix). As the sintering temperature (1075–1200 °C) increased, the 1 kHz response of the ε–T curves of Method-A samples transformed from a single peak to broad-narrow double peaks of high dielectric loss tangent (tan δ). Nonetheless, samples of Method-B possessed a clearly defined transmission electron microscopy (TEM) core-shell structure, flattened double-peak ε-T curves, optimised dielectric properties (ε = ~1563–1851 and tan δ < 1.5% at room temperature), and a wide-ranging temperature behaviour that meets the X8R dielectric standards (ΔC/C25°C < ±15%). The maximum dielectric breakdown strength of Method-B samples reached ~131 kVcm, while the energy storage density was ~0.726 J/cm3 at a maximum efficiency of ~80% at 1100 °C. Thus, exhibiting good potentials for balancing temperature stability with energy storage applications. |