Ultrahigh discharge energy density (W_dis = 10.5 J cm⁻³) and efficiency (η = 87%) have been obtained in doped BiFeO₃–BaTiO₃ ceramic multilayers by achieving an electrically rather than chemically homogeneous microstructure. Back scattered scanning and transmission electron microscopy combined with energy dispersive X-ray spectroscopy mapping of (0.7 − x)BiFeO₃–0.3BaTiO₃–xNd(Zn_0.5Zr_0.5)O₃ (0.05 ≤ x ≤ 0.10) ceramics revealed a core–shell grain structure which switched from a bright to dark contrast as x increased. Compositions with x = 0.08 were at the point of cross over between these two manifestations of core–shell contrast. Dielectric measurements together with the absence of macrodomains in diffraction contrast TEM images suggested that compositions with x = 0.08 exhibited relaxor behaviour within both the core and shell regions. Impedance spectroscopy demonstrated that, despite being chemical dissimilar, the grains were electrically homogeneous and insulating with little evidence of conductive cores. Multilayers of x = 0.08 had enhanced breakdown strength, E_BDS > 700 kV cm⁻¹ and a slim hysteresis loop which resulted in large W_dis and high η which were temperature stable to <15% from 25 to 150 °C.

Bismuth ferrite-based lead-free multilayers with a high recoverable energy density of 6.74 J cm⁻³ and an efficiency of 77%, stable up to 125 °C.

Tailored dopant strategies are proposed to optimise the energy density of BiFeO ₃ –SrTiO ₃ , which can be adapted for other high polarisability oxide-based systems.