Reversible field-induced phase transitions define antiferroelectric perovskite oxides and lay the foundation for high-energy storage density materials, required for future green technologies. However, promising new antiferroelectrics are hampered by transition´s irreversibility and low electrical resistivity. Here, we demonstrate an approach to overcome these problems by adjusting the local structure and defect chemistry, delivering NaNbO₃-based antiferroelectrics with well-defined double polarization loops. The attending reversible phase transition and structural changes at different length scales are probed by in situ high-energy X-ray diffraction, total scattering, transmission electron microcopy, and nuclear magnetic resonance spectroscopy. We show that the energy-storage density of the antiferroelectric compositions can be increased by an order of magnitude, while increasing the chemical disorder transforms the material to a relaxor state with a high energy efficiency of 90%. The results provide guidelines for efficient design of (anti-)ferroelectrics and open the way for the development of new material systems for a sustainable future.

We report an intrinsic strain engineering, akin to thin filmlike approaches, via irreversible high-temperature plastic deformation of a tetragonal ferroelectric single-crystal BaTiO3. Dislocations well-aligned along the [001] axis and associated strain fields in plane defined by the [110]/[1¯10] plane are introduced into the volume, thus nucleating only in-plane domain variants. By combining direct experimental observations and theoretical analyses, we reveal that domain instability and extrinsic degradation processes can both be mitigated during the aging and fatigue processes, and demonstrate that this requires careful strain tuning of the ratio of in-plane and out-of-plane domain variants. Our findings advance the understanding of structural defects that drive domain nucleation and instabilities in ferroic materials and are essential for mitigating device degradation.