Relaxor Research Articles

Enhanced Energy Storage Performance of Lead-Free Sr0.7Bi0.2TiO3 Ceramics via Tape Casting.

Abstract The development of pulsed power technology demands high energy storage density dielectric materials. In this study, Sr0.7Bi0.2TiO3 relaxor ferroelectric ceramic thick films were prepared using a tape-casting process. The ceramics exhibit a dense structure and typical relaxor ferroelectric hysteresis curves, achieving an energy storage density of 4.77 J/cm³ and efficiency of 94.4%, attributed to the high polarization intensity, low remnant polarization, and low hysteresis loss of relaxor ferroelectrics. Additionally, the material demonstrates good temperature stability. Moreover, the Sr0.7Bi0.2TiO3 ceramic thick films show advantages in charge-discharge performance, capable of discharging within hundreds of nanoseconds and achieving a power density of 137 MW/cm³. Overall, the Sr0.7Bi0.2TiO3 ceramic thick film exhibits a comprehensive performance advantage in terms of energy storage density, efficiency, and power density. Additionally, the material was fabricated using the tape-casting process, which is compatible with subsequent multilayer ceramic capacitor (MLCC) production, indicating potential for further performance enhancement.

Multi-scale and time-resolved structure analysis of relaxor ferroelectric crystals under an electric field

Lead-based relaxor ferroelectrics exhibit giant piezoelectric properties owing to their heterogeneous structures. The average and local structures measured by single-crystal X-ray diffraction under DC and AC electric fields are reviewed in this article. The position-dependent local lattice strain and the distribution of polar nanodomains and nanoregions show strong electric field dependence, which contributes to the giant piezoelectric properties.

Large Room-Temperature Electrocaloric Effect in Lead-Free Relaxor Ferroelectric Ceramics with Wide Operation Temperature Range

In order to obtain large room-temperature electrocaloric effect (ECE) and wide operation temperature range simultaneously in lead-free ceramics, we proposed designing a relaxor ferroelectric with a Tm (the temperature at which the maximum dielectric permittivity is achieved) near-room temperature and glass addition. Based on this strategy, we designed and fabricated lead-free 0.76NaNbO3–0.24BaTiO3 (NN-24BT) ceramics with 1wt.% BaO–B2O3–SiO2 glass addition, which showed distinct relaxor ferroelectric characteristics with strongly diffused phase transition and a Tm near-room temperature. Based on a direct measurement method, a large ΔT (adiabatic temperature change) of 1.3 K was obtained at room temperature under a high field of 11.0 kV mm−1. Additionally, large ECE can be maintained (>0.6 K@6.1 kV mm−1) over a broad temperature range from 23 °C to 69 °C. Moreover, the ECE displayed excellent cyclic stability with a variation in ΔT below ±7% within 100 test cycles. The comprehensive ECE performance is significantly better than other lead-free ceramics. Our work provides a general and effective approach to designing lead-free, high-performance ECE ceramics, and the approach possesses the potential to be utilized to improve the ECE performance of other lead-free ferroelectric ceramic systems.

Boosting Energy-Storage in High-Entropy Pb-Free Relaxors Engineered by Local Lattice Distortion.

The high-entropy strategy has shown potential in advancing the energy-storage performance of dielectric capacitors, offering benefits to a range of electronic and electrical systems. However, designing high-performance high-entropy relaxor ferroelectrics (RFEs) presents challenges due to the unclear correlation between their core effects and local polarization heterogeneity. Here, we demonstrate that by engineering the local lattice distortion, a core effect in high-entropy systems, to manipulate the local polarization configuration, a giant energy density (Wrec) of 18.7 J cm-3 and high efficiency (η) of 85% can be achieved in (Bi0.5K0.5)TiO3-based high-entropy bulk RFE ceramics. Atomic-level local structural analysis unveils that the local lattice distortion field can be flattened by introducing ions with less size mismatch. The increase in configurational entropy from 1.54 to 2.06R is associated with a smoother polar displacement vector field and a reduction in the size of polar clusters to several unit-cell sizes with weak coupling. Consequently, a substantial decrease in hysteresis and an enhancement in the breakdown field strength can be obtained, leading to a significant improvement in energy density by over 6 times and efficiency by 3 times. Our research establishes a relationship between local lattice distortion, atomic polar displacement, and energy-storage performance in complex high-entropy systems, providing insights for enhancing energy-storage performance via a local structure design.

Domain Dynamics Response to Polarization Switching in Relaxor Ferroelectrics.

Nanoscale polar regions, or nanodomains (NDs), are crucial for understanding the domain structure and high susceptibility of relaxors. However, unveiling the evolution and function of NDs during polarization switching at the microscopic level is of great challenge. The experimental in situ characterization of NDs under electric-field perturbations, and computational accurate prediction of the dipole switching within a sufficiently large supercell, are notoriously tricky and tedious. These difficulties hinder a full understanding of the link between micro domain dynamics and macro polarization switching. Herein, the real-time evolution of NDs at the nanoscale is observed and visualized during polarization switching in an exemplary relaxor system of Bi5- xLaxMg0.5Ti3.5O15. Two fundamentally different domain switching pathways and dynamic characteristics are revealed: one steep, bipolar-like switching between two degenerate polarization states; and another flat, multi-step switching process with a thermodynamically stable non-polar mesophase mediating the degenerate polarization states. The two are determined by the distinct Landau energy landscapes that are strongly dependent on the intrinsic domain configurations and interdomain interactions. This work bridges the gap between micro domain dynamics and macro polarization switching, providing a guiding principle for the strategic design and optimization of relaxors.

Unleashed Remarkable Energy Storage Performance in Bi0.5K0.5TiO3-based Relaxor Ferroelectrics by Local Structural Fluctuation.

Dielectric capacitors harvest energy through an electrostaticprocess, which enables an ultrafast charging-discharging rate and ultrahigh power density. However, achieving high energy density (Wrec) and efficiency (η) simultaneously, especially when preserving them across a wide frequency/temperature range or cycling numbers, remains challenging. In this work, by especially introducing NaTaO3 into the representative ferroelectric relaxor of Bi0.5K0.5TiO3-Bi0.5Na0.5TiO3 and leveraging the mismatch between B-site atoms, we proposed a method of enhancing local structural fluctuation to refine the polar configuration and to effectively improve its overall energy-storage performances. As a consequence, the ceramic exhibits an ultrahigh Wrec of 15.0 J/cm3 and high η up to 80%, along with a very wide frequency stability of 10 - 200 Hz and extensive cycling number up to 108. In-depth local structure and chemical environment investigations, consisting of atom-scale electron microscopy, neutron total scattering, and solid-state nuclear magnetic resonance, reveal that the randomly distributed A/B-site atom pairs emerge in the system, leading to the evident local structural fluctuations and concomitant polymorphic polar nanodomains. These key ingredients contribute to the large polarization, minimal hysteresis, and high breakdown strength, thereby promoting energy-storage performances. This work opens a new path for designing high-performance dielectric capacitors via manipulating local structural fluctuations.

Unleashed Remarkable Energy Storage Performance in Bi0.5K0.5TiO3‐based Relaxor Ferroelectrics by Local Structural Fluctuation

Unleashed Remarkable Energy Storage Performance in Bi0.5K0.5TiO3‐based Relaxor Ferroelectrics by Local Structural Fluctuation

Ultrahigh Energy-Storage in Dual-Phase Relaxor Ferroelectric Ceramics.

High-performance dielectric energy-storage ceramics are beneficial for electrostatic capacitors used in various electronic systems. However, the trade-off between reversible polarizability and breakdown strength poses a significant challenge in simultaneously achieving high energy density and efficiency. Here a strategy is presented to address this issue by constructing a dual-phase structure through in situ phase separation. (Bi0.5Na0.5)TiO3-BaTiO3-based relaxor ferroelectric ceramics are developed, creating a grain-separated dual perovskite phase structure using a facile solid-state reaction method. These ceramics feature two interactive relaxor phases with diversified nanoscale polar structures and heterogeneous grain boundaries, synergistically contributing to high polarization with low hysteresis, substantially increased resistivity, and suppressed electrostrain. Remarkably, a record-high energy density of 23.6Jcm-3 with a high efficiency of 92% under 99kVmm-1 is achieved in the bulk ceramic capacitor. This strategy holds promise for enhancing overall energy-storage performance and related functionalities in ferroelectrics.

High-performance electric energy storage in BiFeO3–Ba(Ti0.8Zr0.2)O3 relaxor ferroelectric ceramics

Perovskite relaxor ferroelectrics have been widely developed for energy storage applications due to their exceptional dielectric properties. This work explores the energy storage performance, thermal stability, and structural evolution in (1-x)BiFeO3–x Ba(Ti0.8Zr0.2)O3 ceramics (x = 0.3, 0.4, 0.5, and 0.6) via modulating Ba(Ti0.8Zr0.2)O3 (BZT) concentration. An enhancement of breakdown electric field from 120 kV/cm at x = 0.3–220 kV/cm at x = 0.5 can be attributed to increased grain boundaries and nanodomains as electric barriers to inhibit charge mobility. A high recoverable energy density of 5.9 J/cm3 and a high energy efficiency of 86.2 % were achieved at x = 0.5 and 0.6, respectively. The structure shifts from ferroelectric rhombohedral R3c symmetry toward a coexistence of nonpolar symmetries (including tetragonal P4/mmm, cubic Pm-3m, and orthorhombic Pbnm) with increasing BZT. The integration of BZT in BiFeO3 demonstrates to break the long-range order and promote the formation of polar nanoregions and nanodomains, leading to a high-efficiency energy storage.

Integrated structural and functional analysis of Ba1-xSrxTiO3-Bi0.5Na0.5TiO3 ceramics: Insights into energy storage and electrocaloric performance

This paper reports an extensive investigation on the structural, dielectric, ferroelectric and pyroelectric properties of 0.7Ba1-xSrxTiO3 – 0.3Bi0.5Na0.5TiO3 (x = 0.0, 0.5, 0.6, 0.7) ceramics synthesized via conventional solid-state reaction (SSR) technique. X-ray diffraction data confirms the presence of pure perovskite phase. The variation of lattice parameters with strontium concentration in 0.7Ba1-xSrxTiO3 – 0.3Bi0.5Na0.5TiO3 ceramics were evaluated using the Rietveld refinement of the XRD data. The variation of dielectric permittivity with temperature (ε' ∼ T) shows the diffused phase transition and all the parameters related to the relaxor ferroelectrics (relaxation coefficient, activation energy and freezing temperature) were evaluated. The energy storage properties of the as-prepared ceramics were evaluated using the room temperature PE loop. Amongst the as-prepared ceramics, the composition with x = 0.5 possesses the highest energy storage density of 0.46 J/cm3 with an efficiency of 90 %. The temperature dependent P-E loops were used to study the electrocaloric effect (ECE). The ECE calculations were performed using in-direct method based on Maxwell's thermodynamic relations. A maximum adiabatic temperature change of 0.32 K is achieved at 268 K under a small applied electric field of 25 kV/cm for the ceramic with Sr content x = 0.5. Additionally, electrocaloric responsivity ξmax = 0.13 K mm/kV was also found for the studied ceramics. The above results show that the ceramic 0.7Ba1-xSrxTiO3 – 0.3Bi0.5Na0.5TiO3 with the composition x = 0.5 is a viable lead-free option for application in solid state refrigeration.

Deciphering the relationships among phase boundary, domain structure, and excellent electrical properties of ternary Bi0.5Na0.5TiO3-Bi0.2Sr0.7TiO3-NaNbO3 ferroelectrics

Bi0.5Na0.5TiO3-based ferroelectric ceramics have broad application prospects due to their excellent electrical properties and are considered to be one of the most promising functional materials to supersede lead-based materials. Here, 0.9Bi0.5Na0.5TiO3-0.1Bi0.2Sr0.7TiO3-xNaNbO3 (BNT-BST-xNN) ternary lead-free ferroelectric ceramics were prepared, and the origin of their excellent dielectric properties was investigated in terms of phase boundary and domain structure. The introduction of NN led to a phase transition from the ferroelectric rhombohedral phase (R3c) to the relaxor tetragonal phase (P4bm), and the two phases coexisted in the BNT-BST-xNN ternary solid solution with x ranging from 0.06 to 0.2. Meanwhile, the macroscopic domain of BNT-BST was destroyed and replaced by highly active polar nano-regions (PNRs) of the P4bm phase, leading to an increase in local structural disorder and enhanced relaxor behavior. A dielectric constant (εr) of ∼1765 (150 °C) with Δε/ε150 °C less than 15 % over a broad range from 80 to 328 °C was achieved in the BNT-BST-0.15NN, and an excellent energy storage property (Wrec = 3.3 J/cm3) was obtained under a low electric field (190 kV/cm). More specifically, the relationship among phase boundary, domain structure, and excellent electrical properties was achieved based on Rietveld refinements and the dielectric/ferroelectric characterizations. This work provides a deep insight into the phase evolution and its impact on the electrical properties of the BNT-based relaxor ferroelectrics.

Ferroelectric/Piezoelectric Materials in Energy Harvesting: Physical Properties and Current Status of Applications

The inevitable feedback between the environmental and energy crisis within the next decades can probably trigger and/or promote a global imbalance in both financial and public health terms. To handle this difficult situation, in the last decades, many different classes of materials have been recruited to assist in the management, production, and storage of so-called clean energy. Probably, ferromagnets, superconductors and ferroelectric/piezoelectric materials stand at the frontline of applications that relate to clean energy. For instance, ferromagnets are usually employed in wind turbines, superconductors are commonly used in storage facilities and ferroelectric/piezoelectric materials are employed for the harvesting of stray energy from the ambient environment. In this work, we focus on the wide family of ferroelectric/piezoelectric materials, reviewing their physical properties in close connection to their application in the field of clean energy. Among other compounds, we focus on the archetypal compound Pb(Zr,Ti)O3 (or PZT), which is well studied and thus preferred for its reliable performance in applications. Also, we pay special attention to the advanced ferroelectric relaxor compound (1−x)Pb(Mg1/3Nb2/3)O3−xPbTiO3 (or PMN-xPT) due to its superior performance. The inhomogeneous composition that many kinds of such materials exhibit at the so-called morphotropic phase boundary is reviewed in connection to possible advantages that it may bring when applications are considered.

Superior Energy Storage Performances of Aurivillius Relaxor Ferroelectric Films at Medium Electric Field Derived from Insert Layer Engineering

Superior Energy Storage Performances of Aurivillius Relaxor Ferroelectric Films at Medium Electric Field Derived from Insert Layer Engineering

Origin of zero thermal expansion in an average cubic structure in Pb-free relaxor ferroelectrics

This study presents “K0.5Na0.5NbO3-based” Pb-free smart material 0.80(K0.5Na0.5NbO3)–0.20(Ba0.9Sr0.1TiO3) (KBST20) as exhibiting zero thermal expansion (ZTE) at low temperatures (T≤ 100 K) with long-range cubic symmetry stable over a wide temperature range (9 K ≤T≤ 500 K). The linear coefficient of the thermal expansion (αl) obtained from temperature-dependent neutron diffraction data is in the range of 0.255–5.75 × 10−6 K–1 (9–500 K), which is rarely observed for Pb-free materials possessing long-range cubic symmetry. The temperature-dependent dielectric data of KBST20 exhibits a strong relaxational behavior with high frequency dispersion (ΔT≈ 27 K), suggesting the presence of polar phased regions known as polar nano regions. The ZTE has been attributed to enhanced correlations among PNRs exhibiting ferroelectrostriction. Furthermore, temperature-dependent Raman scattering data reveal polar monoclinic distortion at short ranges rather than cubic symmetry at long ranges. In addition, the intensity of Raman modes increases with the decrease in temperature, suggesting enhancement of the polar phase at low temperatures, which consequently leads to zero thermal expansion in KBST20.

Ultrahigh Electrostrictive Effect in Lead-Free Sodium Bismuth Titanate-Based Relaxor Ferroelectric Thick Film.

In recent years, the development of environmentally friendly, lead-free ferroelectric films with prominent electrostrictive effects have been a key area of focus due to their potential applications in micro-actuators, sensors, and transducers for advanced microelectromechanical systems (MEMS). This work investigated the enhanced electrostrictive effect in lead-free sodium bismuth titanate-based relaxor ferroelectric films. The films, composed of (Bi0.5Na0.5)0.8-xBaxSr0.2TiO3 (BNBST, x = 0.02, 0.06, and 0.11), with thickness around 1 μm, were prepared using a sol-gel method on Pt/TiO2/SiO2/Si substrates. By varying the Ba2+ content, the crystal structure, morphology, and electrical properties, including dielectric, ferroelectric, strain, and electromechanical performance, were investigated. The films exhibited a single pseudocubic structure without preferred orientation. A remarkable strain response (S > 0.24%) was obtained in the films (x = 0.02, 0.06) with the coexistence of nonergodic and ergodic relaxor phases. Further, in the x = 0.11 thick films with an ergodic relaxor state, an ultrahigh electrostrictive coefficient Q of 0.32 m4/C2 was achieved. These findings highlight the potential of BNBST films as high-performance, environmentally friendly electrostrictive films for advanced microelectromechanical systems (MEMS) and electronic devices.

A highly polarizable concentrated dipole glass for ultrahigh energy storage

Relaxor ferroelectrics are highly desired for pulse-power dielectric capacitors, however it has become a bottleneck that substantial enhancements of energy density generally sacrifice energy efficiency under superhigh fields. Here, we demonstrate a novel concept of highly polarizable concentrated dipole glass in delicately-designed high-entropy (Bi1/3Ba1/3Na1/3)(Fe2/9Ti5/9Nb2/9)O3 ceramic achieved via substitution of multiple heterovalent ferroelectric-active principal cation species on equivalent lattice sites. The atomic-scaled polar heterogeneity of dipoles with different polar vectors between adjacent unit cells enables diffuse reorientation process but disables appreciable growth with electric fields. These unique features cause superior recoverable energy density of ~15.9 J cm−3 and efficiency of ~93.3% in bulk ceramics. We also extend the highly polarizable concentrated dipole glass to the prototype multilayer ceramic capacitor, which exhibits record-breaking recoverable energy density of ~26.3 J cm−3 and efficiency of ~92.4% with excellent temperature and cycle stability. This research presents a distinctive approach for designing high-performance energy-storage dielectric capacitors.

High energy storage performance of KNN-based relaxor ferroelectrics in multiphase-coexisted superparaelectric state

Although K0.5Na0.5NbO3 (KNN) possesses large maximum polarization and relatively high breakdown strength, the large remnant polarization constrains their practical applications as energy storage materials. In this work, through multi-element doping, (K0.5−0.5xNa0.5−0.5xBix)(Nb1−xSn0.2xZn0.6xTa0.2x)O3 relaxor ferroelectrics were prepared. As the superparaelectric states (SPE) were adjusted to room temperature, orthorhombic, tetragonal, and cubic phases coexisted, accompanied by the highly dynamic polar nanoregions (PNRs). In particular, a high recoverable energy storage density of 4.5 J/cm3 and an energy storage efficiency of 83% were achieved for the x = 0.125 ceramic, with the variations less than 11% and 4%, respectively, in the wide temperature range of 20–180 °C. These results demonstrate that the multiphase PNRs in the SPE state is an effective strategy for improving the energy storage performance of KNN-based ceramics.

Realizing enhanced energy storage performance of Na0.47Bi0.47Ba0.06TiO3-based relaxors with weak coupling behavior by manipulating phase fraction

Lead-free dielectric capacitors have attracted considerable attention as the core energy storage element of pulsed power systems due to their advantages of fast charging capability, high power density and environmental friendliness. However, the low recoverable energy storage density (Wrec) and narrow operating temperature range have become the bottleneck technical problems limiting its practical application. In this work, a class of weakly coupled relaxor ferroelectrics with excellent Wrec (9.06 J/cm3) and energy storage efficiency (η ∼ 85.3 %) were designed and prepared by manipulating phase fraction. Moreover, the materials exhibit excellent temperature stability with regard to energy storage, with a change in Wrec and η of less than 8 % over a wide temperature range (25 °C − 200 °C). The introduction of Sm(Mg0.5Hf0.5)O3 (SMH) enhances the insulating properties while refining the grains, effectively increasing the breakdown field strength (Eb) of the material. The emergence of weakly coupled nano-microdomains has the effect of suppressing the nonlinear polarization response of the material, which in turn results in a high polarization difference (ΔP). The preceding work presents a universal strategy for the future design and preparation of BNT-based lead-free dielectric capacitors with high energy storage properties (ESP) and good temperature stability.

(Invited) Modification of Dielectric Properties of Film Dielectric Materials by Solid Solution System

Compound semiconductor based power devices such as SiC and GaN require high temperature operating passive devices such as a capacitor. SiC-based active devices can operate above 250 °C. The development of high-temperature operational passives is urgently needed to advance to the module and system level. In the case of capacitors, currently available capacitors can only operate efficiently up to 175 °C. Therefore, a thin film capacitor that can operate at high temperatures and be monolithically integrated near the active device should be developed. In this talk, I will present our achievements in the development of high-temperature operating dielectric film materials using the solid solution system. One topic is A2B2O7 pyrochlore ferroelectrics. The ferroelectric materials with the pyrochlore structure such as Sr2Nb2O7 exhibited the high dielectric constant above 100 at high and low temperature ranges. However, due to the crystallographic direction dependence of the Curie-Weiss temperature, the temperature stability of the dielectric constant from room temperature to 300 °C was not available. In order to obtain the high temperature stability of dielectric constant from room temperature to 300 °C with high dielectric constant over 100, the pyrochlore ferroelectric solid solution thin films were investigated by employing the combinatorial synthesis. Composition spread thin films of solid solution of two or three kinds of materials were deposited on substrates by physical vapor deposition technique, which provided the systematic physical properties. High-throughput combinatorial synthesis method is effective in the rapid optimization of the correlation between the crystallization and the dielectric property change behavior. For the composition spread solid solution film, the Sr- or La-containing A2B2O7 pyrochlore ferroelectrics were selected from the viewpoints of ion radios and crystallographic direction dependence of the Curie-Weiss temperature. The composition spread films were formed on a Pt/Ti/SiO2/Si substrate by combinatorial RF sputtering with stoichiometric composition targets. The X-ray fluorescence spectrum of the composition-spread film showed a linear variation of the metal composition. After deposition, the samples were annealed at different temperatures under oxygen atmosphere to reduce oxygen vacancies and improve crystallinity. The crystallization of the composition-spread solid solution thin film was confirmed by X-ray diffraction patterns, indicating the composition dependence of the crystallographic orientation. Some compositions showed high dielectric constant over 100 and high temperature stability from room temperature to 300 °C. In the presentation, the correlation between film composition, orientation and dielectric constant will be discussed in detail. In the presentation, we also introduce our achievement of the BaTiO3 based relaxor ferroelectrics and other dielectric materials development using the solid solution system. For the relaxor ferroelectrics, among the BaTiO3 based relaxor ferroelectrics, we have selected x[BaTiO3]-(1-x)[Bi(Mg2/3Nb1/3)O3] . The permittivity of 400 and the stability <8% from room temperature to 400 °C were obtained, which are promising as high-temperature dielectric medium.

Enhancing comprehensive energy storage properties in Pb-free relaxor AFE/FE system via heterogeneous structure tuning and defect engineering

Multi-phase NaNbO3 (NN) exhibits high adjustability on the ordering of both polarization and oxygen octahedral tilt, becoming a perfect carrier to design heterogeneous structure for boosting comprehensive energy storage properties. To balance the energy storage density and efficiency, the coexistence of the relaxor antiferroelectric (AFE) with high polarization capability and the relaxor ferroelectrics (RFE) with high efficiency is designed in this work by introducing Sr0.7Bi0.2□0.1Ti0.75Ta0.2□0.05O3 (SBTT) into NaNbO3-BiFeO3. As a result, an outstanding capacitive energy density (Wrec) of 12.25 J cm−3 with a high η of 83 % can be achieved in NN-BF-SBTT ceramic, which can be identified as a novel heterogeneous coexisting structure with the crossover of high polarization capability in relaxor AFE and high efficiency in RFE in terms of high-resolution TEM. Furthermore, grain refinement and the dense structure inhibit the leak current, suppress the concentration of oxygen vacancy defects and raise the activation energy (Ea), thus enhancing the EB. These excellent energy storage properties overcome the trade-offs between the two sets of parameters (Wrec-η, ΔP-EB), offering a refreshing strategy for the development of high-performance ceramic capacitors.