In response to the current environmental regulations against the use of lead in daily electronic devices, a number of investigations have been performed worldwide in search for alternative piezoelectric ceramics that can replace the marketdominating lead-based ones, representatively Pb(Zr x Ti 1-x )O 3 (PZT)-based solid solutions. Selected systems of potential importance such as chemically modified and/or crystallographically textured (K, Na)NbO 3 and (Bi 1/2 Na 1/2 )TiO 3 -based solid solutions have been developed. Nevertheless, only few achievements have so far been introduced to the marketplace. A recent discovery has greatly extended our tool box for material design by furnishing (Bi 1/2 Na 1/2 )TiO 3 -based ceramics with a reversible phase transition between an ergodic relaxor state and a ferroelectric with the application of electric field. This paired the piezoelectric effect with a strain-generating phase transition and extended opportunities for actuator applications in a completely new manner. In this contribution, we will present the status and perspectives of this new class of actuator ceramics, aiming at covering a wide spectrum of topics, i.e., from fundamentals to practice.

Environment‐friendly lead‐free piezoelectric ceramics have been studied extensively in the past decade with great progress particularly in systems based on a niobate perovskite compound formulated as (K, Na)NbO3 (abbreviated as KNN). A comprehensive review on the latest development of KNN‐based piezoelectric ceramics is presented in this article, including the phase structure, property enhancement approaches, and sintering processes as well as the status of some promising applications. The phase structure of KNN was reexamined and associated with the effect of chemical modification on its tetragonal‐to‐orthorhombic transition. Then, a special focus is placed on the temperature dependence of piezoelectric properties of KNN‐based ceramics, followed by reviewing the recent approaches devoted to the temperature‐stability enhancement. The processing fundamentals related to the sintering of KNN‐based ceramics are also presented with an emphasis on compositional and microstructural control. Finally, this review introduces several industrial attempts of traditional piezoceramic products using KNN‐based ceramics and the studies on some promising application in authors' laboratory.

The development of lead‐free piezoceramics has attracted great interest because of growing environmental concerns. A polymorphic phase transition (PPT) has been utilized in the past to tailor piezoelectric properties in lead‐free (K,Na)NbO3 (KNN)‐based materials accepting the drawback of large temperature sensitivity. Here a material concept is reported, which yields an average piezoelectric coefficientd33 of about 300 pC/N and a high level of unipolar strain up to 0.16% at room temperature. Most intriguingly, field‐induced strain varies less than 10% from room temperature to 175 °C. The temperature insensitivity of field‐induced strain is rationalized using an electrostrictive coupling to polarization amplitude while the temperature‐dependent piezoelectric coefficient is discussed using localized piezoresponse probed by piezoforce microscopy. This discovery opens a new development window for temperature‐insensitive piezoelectric actuators despite the presence of a polymorphic phase transition around room temperature.

Aging and re‐poling induced enhancement of piezoelectricity are found in (K,Na)NbO3 (KNN)‐based lead‐free piezoelectric ceramics. For a compositionally optimized Li‐doped composition, its piezoelectric coefficient d33 can be increased up to 324 pC N−1 even from a considerably high value (190 pC N−1) by means of a re‐poling treatment after room‐temperature aging. Such a high d33 value is only reachable in KNN ceramics with complicated modifications using Ta and Sb dopants. High‐angle X‐ray diffraction analysis reveals apparent changes in the crystallographic orientations related to a 90° domain switching before and after the aging and re‐poling process. A possible mechanism considering both defect migration and rotation of spontaneous polarization explains the experimental results. The present study provides a general approach towards piezoelectric response enhancement in KNN‐based piezoelectric ceramics.