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0.9Ba(Ti1−xMgx)O3−x-0.1NaNbO3 (BTNN-100xMg) solid solutions are investigated with a view to developing Bi, Pb, and rare earth free, high voltage multilayer ceramic capacitors. Mg doping on the B-site significantly reduced the electronic conductivity and resulted in ceramics that could withstand a pulsed unipolar field of >300 kV/cm (Emax) to give a recoverable energy density of 3.4 J/cm3 at 82.6% efficiency for x = 0.01. The high Emax is accompanied by a high dielectric permittivity (ε′ ∼ 1700 at room temperature) with temperature-stable dielectric permittivity of Δε/ε298K ≤ ±15% and loss tangent tan δ < 0.02 from 116 to 378 K, corresponding to an X6R designation in the Electronic Industry Alliance codes.

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