Recent development in lead-free perovskite piezoelectric bulk materials

High strain piezoelectric ceramics are the state-of-the-art materials for high precision, positioning devices. A comprehensive review of the latest developments of the various types of perovskite piezoelectric ceramic systems is presented herein, with special attention given to three promising families of lead-free perovskite ferroelectrics: the barium titanate, alkaline niobate and bismuth perovskites. Included in this review are details of phase transition behavior, strain enhancement approaches, material reliabilities as well as the status of some promising applications. This current review describes both compositional and structural engineering approaches that are intended to achieve enhanced strain properties in perovskite piezoelectric ceramics. The factors that affect the strain behavior of high-strain perovskite piezoelectric ceramics are addressed. The reliability characteristics of these high-strain ferroelectrics as well as the recent approaches to the long-term electrical, thermal and time-stability enhancement are summarized. Several promising applications of high-strain perovskite materials are introduced, which take advantages of their characteristics; examples include high-energy storage, pyroelectric and electro-caloric effect and luminescent properties.

Progress in high-strain perovskite piezoelectric ceramics

The development of lead-free bulk ceramics with high recoverable energy density (Wrec) is of decisive importance for meeting the requirements of advanced pulsed power capacitors toward miniaturization and integration. However, the Wrec (<2 J cm−3) of lead-free bulk ceramics has long been limited by their low dielectric breakdown strength (DBS < 200 kV cm−1) and small saturation polarization (Ps). In this work, a strategy (compositions control the grain size of lead-free ceramics to submicron scale to increase the DBS, and the hybridization between the Bi 6p and O 2p orbitals enhances the Ps) was proposed to improve the Wrec of lead-free ceramics. (K0.5Na0.5)NbO3–Bi(Me2/3Nb1/3)O3 solid solutions (where Me2+ = Mg and Zn) were designed for achieving large Ps, and high DBS and Wrec. As an example, (1 − x)(K0.5Na0.5)NbO3–xBi(Mg2/3Nb1/3)O3 (KNN–BMN) ceramics were prepared by using a conventional solid-state reaction process in this study. Large Ps (41 μC cm−2) and high DBS (300 kV cm−1) were obtained for 0.90KNN–0.10BMN ceramics, leading to large Wrec (4.08 J cm−3). The significantly enhanced Wrec is more than 2–3 times larger than that of other lead-free bulk ceramics. The findings in this study not only provide a design methodology for developing lead-free bulk ceramics with large Wrec but also could bring about the development of a series of KNN-based ceramics with significantly enhanced Wrec and DBS in the future. More importantly, this work opens a new research and application field (dielectric energy storage) for (K0.5Na0.5)NbO3-based ceramics.

Potassium–sodium niobate based lead-free ceramics: novel electrical energy storage materials

Simultaneously achieved temperature-insensitive high energy density and efficiency in domain engineered BaTiO3-Bi(Mg0.5Zr0.5)O3 lead-free relaxor ferroelectrics

With growing concern over world environmental problems and increasing legislative restriction on using lead and lead-containing materials, a feasible replacement for lead-based piezoceramics is desperately needed. Herein, we report a large piezoelectric strain (d33*) of 470 pm/V and a high Curie temperature (Tc) of 243 °C in (Na0.5K0.5)NbO3-(Bi0.5Li0.5)TiO3-BaZrO3 lead-free ceramics by doping MnO2. Moreover, excellent temperature stability is also observed from room temperature to 170 °C (430 pm/V at 100 °C and 370 pm/V at 170 °C). Thermally stimulated depolarization currents (TSDC) analysis reveals the reduced defects and improved ferroelectricity in MnO2-doped piezoceramics from a macroscopic view. Local poling experiments and local switching spectroscopy piezoresponse force microscopy (SS-PFM) demonstrates the enhanced ferroelectricity and domain mobility from a microscopic view. Distinct grain growth and improvement in phase angle may also account for the enhancement of piezoelectric properties.

High and Temperature-Insensitive Piezoelectric Strain in Alkali Niobate Lead-free Perovskite

High piezoelectricity of (K,Na)NbO3 (KNN) lead-free materials benefits from a polymorphic phase transition (PPT) around room temperature, but its temperature sensitivity has been a bottleneck impeding their applications. We find that good thermal stability can be achieved in CaZrO3-modified KNN lead-free piezoceramics, in which the normalized strain d33* almost keeps constant from room temperature up to 140 oC. In situ synchrotron X-ray diffraction experiments combined with permitivity measurements disclose the occurrence of a new phase transformation under an electrical field, which extends the transition range between tetragonal and orthorhombic phases. It is revealed that such an electrically-enhanced diffused polymorphic phase transition (EED-PPT) contributed to the boosted thermal stability of KNN based lead-free piezoceramics with high piezoelectricity. The present approach based on phase engineering should also be effective in endowing other lead-free piezoelectrics with high piezoelectricity and good temperature stability.

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Yu‐Dong Hou

Papers

Diffused Phase Transition Boosts Thermal Stability of High-Performance Lead-Free Piezoelectrics