Perovskite lead-free dielectrics for energy storage applications

We present a critical review that encompasses the fundamentals and state-of-the-art knowledge of barium titanate-based piezoelectrics. First, the essential crystallography, thermodynamic relations, and concepts necessary to understand piezoelectricity and ferroelectricity in barium titanate are discussed. Strategies to optimize piezoelectric properties through microstructure control and chemical modification are also introduced. Thereafter, we systematically review the synthesis, microstructure, and phase diagrams of barium titanate-based piezoelectrics and provide a detailed compilation of their functional and mechanical properties. The most salient materials treated include the (Ba,Ca)(Zr,Ti)O3, (Ba,Ca)(Sn,Ti)O3, and (Ba,Ca)(Hf,Ti)O3 solid solution systems. The technological relevance of barium titanate-based piezoelectrics is also discussed and some potential market indicators are outlined. Finally, perspectives on productive lines of future research and promising areas for the applications of these ma...

BaTiO3-based piezoelectrics: Fundamentals, current status, and perspectives

High-Performance Dielectric Ceramic Films for Energy Storage Capacitors: Progress and Outlook

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 utilization of antiferroelectric (AFE) materials is thought to be an effective approach to enhance the energy density of dielectric capacitors. However, the high energy dissipation and inferior reliability that are associated with the antiferroelectric-ferroelectric phase transition are the main issues that restrict the applications of antiferroelectric ceramics. Here, simultaneously achieving high energy density and efficiency in a dielectric ceramic is proposed by combining antiferroelectric and relaxor features. Based on this concept, a lead-free dielectric (Na0.5 Bi0.5 )TiO3 -x(Sr0.7 Bi0.2 )TiO3 (NBT-xSBT) system is investigated and the corresponding multilayer ceramic capacitors (MLCCs) are fabricated. A record-high energy density of 9.5 J cm-3 , together with a high energy efficiency of 92%, is achieved in NBT-0.45SBT multilayer ceramic capacitors, which consist of ten dielectric layers with the single-layer thickness of 20 µm and the internal electrode area of 6.25 mm2 . Furthermore, the newly developed capacitor exhibits a wide temperature usage range of -60 to 120 °C, with an energy-density variation of less than 10%, and satisfactory cycling reliability, with degradation of less than 8% over 106 cycles. These characteristics demonstrate that the NBT-0.45SBT multilayer ceramic is a promising candidate for high-power energy storage applications.

Multilayer Lead-Free Ceramic Capacitors with Ultrahigh Energy Density and Efficiency.

Polymer based composites with high dielectric constant were successfully fabricated using BaTiO3 nanowires with high aspect ratio as inorganic filler and PVDF-HFP as polymer matrix. PVDF-HFP/BaTiO3 nanoparticles composites were also prepared as a contrast. The BaTiO3 nanowires were synthesized via one-step hydrothermal method. The BaTiO3 nanowires and its two types of composites were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. For the composites, breakdown strength measurements, tensile tests and broadband dielectric spectroscopy analyses were also carried out. The results show that the two types of fillers are homogeneously dispersed in the matrix. The dielectric constant of composites filled by BaTiO3 nanowires is larger than that filled by BaTiO3 nanoparticles at the same content. Stronger interfacial polarization was found in PVDF-HFP/BaTiO3 nanowire composites. Two theoretical models were employed to predict the dielectric constants of composites, and the experimental data were consistent with the estimated trend. The enhanced dielectric properties of PVDF-HFP/BaTiO3 nanowire composites are attributed to the superior interfacial polarization and high aspect ratio of BaTiO3 nanowires.

Enhanced dielectric properties of PVDF-HFP/BaTiO3-nanowire composites induced by interfacial polarization and wire-shape

The improvement of the electrocaloric effect (ECE) in (1−x)(Na0.5Bi0.5)TiO3−xSrTiO3 (NBT-ST) lead-free relaxor ferroelectric ceramics was determined by indirect measurements method and is reported here. The phase transition temperature can be reduced to room temperature by tuning the compositions of the (1−x)NBT-xST material. A large ECE (ΔTmax = 1.64 K, ΔSmax = 2.52 K and ΔT/ΔE = 0.33 K mm kV−1 at 50 kV cm−1) was obtained at 60 °C when x = 0.25. A suitable response over a broad temperature range from 30 °C to 70 °C can be obtained with x = 0.26 with very high cooling values (ΔT > 1 K). In addition, the 0.7NBT-0.3ST AFE-like bulk ceramic exhibited excellent temperature stability in its energy-storage properties from room temperature to 120 °C. The maximum value of the recoverable energy density was 0.65 J/cm3 obtained at 65 kV/cm. Taken together, these properties signified that (1−x)NBT-xST is a promising material for applications in cooling systems and energy-storage in the room temperature range.

Large electrocaloric response and high energy-storage properties over a broad temperature range in lead-free NBT-ST ceramics

High Energy Storage Performance of Opposite Double-Heterojunction Ferroelectricity–Insulators

In this letter, we propose an effective route to obtain large recoverable strain, purely electrostrictive effects and high energy-storage density by inducing defect dipoles into Na0.5Bi0.5TiO3 (NBT)-based relaxor ferroelectrics. It has been found that pinched and double polarization hysteresis loops with high maximum polarization (Pmax) and negligible remanent polarization (Pr) can be observed due to the presence of acceptor-induced defect dipoles. A large recoverable strain of 0.24% with very little hysteresis and high electrostriction coefficient of 0.022 m4 C2 with purely electrostrictive characteristics were acquired when 11 mol. ‰ Mn-doped. Meanwhile, a high recoverable energy density of 1.06 J/cm3 with excellent temperature stability was obtained at the same composition owing to the enlarged value of Pmax-Pr (36.8 μC/cm2) and relatively high electric field (95 kV/cm). Our achievement can open up the exciting opportunities for ferroelectric materials in high-precision positioning devices and high ele...

Tiandong Zhang

Papers

Enhanced dielectric properties of PVDF-HFP/BaTiO3-nanowire composites induced by interfacial polarization and wire-shape

Large electrocaloric response and high energy-storage properties over a broad temperature range in lead-free NBT-ST ceramics

High Energy Storage Performance of Opposite Double-Heterojunction Ferroelectricity–Insulators

Defect dipole induced large recoverable strain and high energy-storage density in lead-free Na0.5Bi0.5TiO3-based systems

High-Energy Storage Density and Efficiency of (1−x)[0.94 NBT–0.06 BT]–xST Lead-Free Ceramics