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.

Here, we introduce phase change mechanisms in lead-free piezoceramics as a strategy to utilize attendant volume change for harvesting large electrostrain. In the newly developed (K,Na)NbO₃ solid-solution at the polymorphic phase boundary we combine atomic mapping of the local polar vector with in situ synchrotron X-ray diffraction and density functional theory to uncover the phase change and interpret its underlying nature. We demonstrate that an electric field-induced phase transition between orthorhombic and tetragonal phases triggers a dramatic volume change and contributes to a huge effective piezoelectric coefficient of 1250 pm V⁻¹ along specific crystallographic directions. The existence of the phase transition is validated by a significant volume change evidenced by the simultaneous recording of macroscopic longitudinal and transverse strain. The principle of using phase transition to promote electrostrain provides broader design flexibility in the development of high-performance piezoelectric materials and opens the door for the discovery of high-performance future functional oxides.

An ultrahigh electric field–induced strain of 0.9% (under 1 kV mm ⁻¹ ) is achieved in lead-free ferroelectric crystals.