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.

The electric field response of the lead-free solid solution (1−x)Bi0.53Na0.47TiO3–xBaTiO3 (BNT–BT) in the higher BT composition range with x = 0.12 was investigated using in situ synchrotron X-ray powder diffraction. An introduced Bi-excess non-stoichiometry caused an extended morphotropic phase boundary, leading to an unexpected fully reversible relaxor to ferroelectric (R–FE) phase transformation behavior. By varying the field frequency in a broad range from 10−4 up to 102 Hz, BNT–12BT showed a frequency-dependent gradual suppression of the field induced ferroelectric phase transformation in favor of the relaxor state. A frequency triggered self-heating within the sample was found and the temperature increase exponentially correlated with the field frequency. The effects of a lowered phase transformation temperature TR–FE, caused by the non-stoichiometric composition, were observed in the experimental setup of the freestanding sample. This frequency-dependent investigation of an R–FE phase transformation is unlike previous macroscopic studies, in which heat dissipating metal contacts are used.

Microstructural design is a widespread approach to tailor the properties of functional materials, with the size effect being an effective constraint that modifies physical phenomena. In this work, we investigate the grain size effect on the properties and the electric field-induced phase transformation behaviour in barium titanate. A broad range of unimodal average grain size distribution between 0.4 µm and 15 µm were successfully sintered avoiding abnormal grain growth. Samples with a grain size close to the range of 1 to 2 µm, balancing microstructural strain, presence and mobility of domain walls to allow the field induced crystal phase transformation, showed optimal electromechanical and dielectric properties. By means of in situ high energy X-ray diffraction and a high-resolution multianalyser detector we distinguish and quantify a tetragonal-orthorhombic phase transformation induced by an electric field, providing unambiguous proof of this induced phase transformation. These results contribute to the understanding of fundamental questions about the piezoelectric effect in barium titanate and consequently other similar systems.