Double Hysteresis Loops Research Articles

Improved energy storage properties in Pb0.82La0.12(ZrxTi1-x)O3 antiferroelectric films with different Zr/Ti ratios

Antiferroelectric (AFE) materials attract widespread attention due to their unique behavior under electric field. In this work, the Pb0.82La0.12(ZrxTi1-x)O3 (PLZT) films with Zr/Ti ratios close to the AFE region are deposited on the LaNiO3/SiO2/Si substrate through chemical deposition method. The dielectric, leakage, and ferroelectric performance of PLZT films are thoroughly examined. It can be concluded that the Zr content in PLZT films can effectively regulate their dielectric properties. At the same time, the increase of Zr/Ti ratio makes the double hysteresis loop of PLZT more obvious, leading to greater stability of the AFE phase, providing a significant advantage in energy storage. Notably, the PLZT film with a Zr/Ti ratio of 95/5 exhibits the highest recoverable energy storage density (Wrec) of 30.8 J/cm3 and energy storage efficiency (η) of 71.5 %. These results reveal that the Zr/Ti ratio in PLZT antiferroelectric films plays a critical role in enhancing their energy storage performance.

Exploring anti-ferroelectric thin films with high energy storage performance by moderating phase transition

Anti-ferroelectric thin films are renowned for their signature double hysteresis loops and sheds light on the distinguished energy storage capabilities of dielectric capacitors in modern electronic devices. However, anti-ferroelectric capacitors are still facing the dual challenges of low energy density and efficiency to achieve state-of-the-art performance. Their large hysteresis and sharp first-order phase transition usually results in a low energy storage efficiency and easy breakdown, severely obscuring its future application. In this study, we demonstrate that anti-ferroelectric (Pb0.97La0.02)(Zr1−xSnx)O3 epitaxial thin films exhibit enhanced energy storage performance through local structural heterogeneity to moderate the first-order phase transition by calculating the corresponding polarization as a function of switching time for the first time. The films exhibit remarkable enhanced breakdown strength (∼3.47 MV/cm, ∼5 times the value for PbZrO3) and energy storage performance. Our endeavors have culminated in the ingenious formulation of a novel strategy, namely, the postponement of polarization processes, thereby elevating the breakdown strength and total energy storage performance. This landmark achievement has unveiled a fresh vista of investigative opportunities for advancing the energy storage prowess of electric dielectrics.

Insight into electronic and magnetic properties of Ba2NiOsO6 double perovskite: A Monte Carlo study and a comparative investigation between TB-mBJ and GGA+U

The structural, electronic, and magnetic properties of the Ba2NiOsO6 double perovskite were comprehensively studied using density functional theory (DFT) and Monte Carlo simulations. Based on DFT calculations, we found that the double perovskite is stable in the ferromagnetic phase. The compound exhibited thermodynamic stability, confirmed by its negative formation energy and phonon spectrum. The electronic and magnetic properties were analyzed using various approximations, including the Generalized Gradient Approximation (GGA), modified Becke–Johnson approximation (mBJ), and Hubbard correction (GGA+U). The electronic profile indicated a metallic nature with GGA and a half-metallic nature with GGA+U and mBJ. The total magnetic moment was approximately 4 μB across all approximations. The Monte Carlo simulations revealed intriguing phenomena, such as a tri-critical point, second-order and first-order phase transitions, a reentrant phenomenon, and both simple and double hysteresis loops.

Revealing the role of B-site cations in the antiferroelectricity of NaNbO3-based perovskites

The promising prospects of antiferroelectric perovskite oxides in the realm of energy storage applications hinge on the unique field-induced phase transitions. Once the transition is triggered by the application of an electric field, characteristic double polarization loops appear. However, NaNbO3-based materials that exhibit a reversible phase transition are still rare, which hinders the practical applications of lead-free antiferroelectrics. Here, the impact of materials chemistry on the competition between antiferroelectric and ferroelectric states is demonstrated in a series of NaNbO3-based solid solutions with varying perovskite B-site cations, while the A-site is fixed as strontium. The crystal structure is analyzed on the basis of Rietveld refinement of high-energy X-ray diffraction data. The phase transition behavior as well as the antiferroelectric and ferroelectric properties are probed by a series of electrical measurements. The antiferroelectric phase is universally observed for all investigated materials in the virgin state. The SrTiO3-substituted system shows an irreversible phase transition similar to that of pure NaNbO3. In contrast, double polarization hysteresis loops are observed in the SrHfO3-, SrZrO3-, and SrSnO3-substituted systems. It is confirmed that compounds that can reduce the tolerance factor of the system contribute to the stabilization of the antiferroelectric order, while those that can reduce the electronegativity difference lead to more pronounced double loops. The competition between antiferroelectricity and ferroelectricity is linked to the competition between covalent and ionic bonding in perovskites.

Component design for stabilizing P phase in NaNbO3-based ceramics and the energy storage performance

Antiferroelectric (AFE) ceramic dielectrics are widely recognized for their high potential in high-power pulse equipment applications. Lead-free NaNbO3 (NN) antiferroelectric ceramics have emerged as a prominent research topic in the field of energy storage due to their abundant phase structure, affordability, and moderate bandgap. The metastable ferroelectric Q phase results in a square hysteresis loop for NN at room temperature. However, 0.96NaNbO3-0.04 CaZrO3 (NNCZ) exhibits a typical double hysteresis loop at room temperature with the main crystalline phase being the antiferroelectric P phase, which has poor energy storage performance. In this study, Bi0.5Na0.5TiO3 (BNT) is used to optimize the energy storage performance and stabilize the P phase in NNCZ simultaneously. The dielectric constant and temperature-dependence XRD results that from −100 °C to 350 °C, x = 0.05 undergoes a phase transition from AFE P to AFE R and then to PE S. The solid solution of BNT decreased the sintering temperature of NN-based ceramics and decreased average grain size, thereby facilitating domain size reduction and improving the sample's energy storage efficiency from ∼30 % to ∼60 %, with an effective energy storage density reaching 1.51 J/cm3. The above results demonstrate that enhancing energy storage efficiency can be achieved through component design by reducing average grain size.

Enhancing Short-Range Interactions to Broaden the Temperature Range for Coexistence of Antiferroelectricity and Ferroelasticity.

Antiferroelectric (AFE) materials, characterized by double electric hysteresis loops, can be transformed to the ferroelectric (FE) phase under an external electric field, making them promising candidates for electronic energy storage and solid-state refrigeration. Additionally, the field-induced strain in AFE materials is contingent upon the direction of the electric field, rendering it with a switching characteristic. Although AFE materials have made progress in the field of energy storage and negative electrocaloric effect, the coexistence of AFE and ferroelasticity is still rarely reported. Here, two isomorphic organic-inorganic hybrid perovskites, HDAEPbCl4 and HDAEPbBr4 (HDAE is [2-(hydroxydimethylammonio)ethan-1-aminium]), exhibiting FE-AFE-PE (PE is paraelectric) phase transitions, are presented. Remarkably, the temperature range where AFE and ferroelasticity coexist is significantly broadened from 59.9 K to 115.1 K by strengthening short-range forces via halogen substitution. This discovery extends the family of FE, AFE, and ferroelastic materials, contributing to the development of multifunctional materials and advancing multifunctional material development.

Simplicial epidemic model with individual resource

The investment and rational use of medical resources are crucial for the prevention and control of epidemics. Here we propose a coupled dynamics model of individual resource and disease transmission on simplicial complexes that considers the dynamic changes of resource quantity during the spreading of the epidemic. Firstly, we derive the solutions (infection density) of the disease transmission dynamics equations under the mean-field approximation, and analyze their stability. We find that the number of stable solutions is related to the infection rates of both interactions and higher-order interactions, and we obtain the transmission threshold under different initial infection densities. Secondly, in the numerical simulation, we discover a double hysteresis loop of infection density as it evolves with the infection rate of interactions. Moreover, we find a critical value for the cost of disease recovery; when the recovery cost is above this critical value, the system state transitions from partial infection to complete infection. Interestingly, we find a maximum value for infection density when the system is in partial infection state. Finally, we verify the existence of the double hysteresis loop on real-world networks.

Ultra-high electrostrain in flux-grown (Bi0.5Na0.5)TiO3-0.06BaTiO3-0.03(K0.5Na0.5)NbO3 single crystals around the nonergodic/ergodic crossover region

In this study, we successfully grew large-sized single crystals (12 × 11 × 8 mm³) of 0.91Bi0.5Na0.5TiO3-0.06BaTiO3-0.03(K0.5Na0.5)NbO3 (BNT-6BT-3KNN) with a <100>c orientation using the flux growth method. This marks the first instance of achieving such crystals. The single crystals display double hysteresis loops, featuring a maximum polarization of ∼64.6 μC/cm2. Capitalizing on the nonergodic/ergodic boundary, the single crystals exhibit a substantial strain (Sm) of 0.91% at the maximum electric field of 20 kV/cm and an exceptionally high inverse piezoelectric coefficient d33* of 4550 pm/V. The creation of long-range domains from needle-like nanodomains and polar-nano regions under the application of an electric field was confirmed through bright-field transmission electron microscopy and piezoresponse force microscopy analyses. The phase diagram for BNT-6BT-3KNN single crystals was constructed by analyzing the temperature dependence of dielectric, ferroelectric, and electrostrain behaviors.

Double hysteresis (P-E) loops in the transparent composite containing BaTiO3 at room temperature

A transparent composite sample containing BaTiO3 was synthesized by using the melting quenching method. The presence of a glassy phase in this composite sample was detected through XRD analysis, and this was further confirmed by DSC study. TEM and SAED analyses provided evidence that the BaTiO3 nanoparticles/clusters are embedded within the borate glass matrix, establishing the composite nature of this sample. FTIR spectrum of the present sample revealed that the glass matrix is composed of two structural groups (BO3 with NBO’s, and BO4), along with the distinct groups for BaTiO3. XPS spectra of the present composite sample indicated the presence of more than one type of boron, barium, titanium and oxygen. DSC and dielectric studies of the present composite sample revealed the presence of the phase transition temperature (Tc). Dielectric constant (ɛr) and dielectric loss (tan δ) curves of the present composite sample displayed an anomaly peak in the vicinity of TC. The optical transmission spectrum of the present composite sample exhibit two transmission bands of Ti3+ (3d1) ions in tetragonal distorted sites. At room temperature, the present transparent composite sample exhibited double hysteresis loops for BaTiO3 at low electric fields. The results obtained can be used for the development of lead-free ferroelectric material.

Design, synthesis and Characterization of a novel antiferroelectric solid solution (1-x)PbHfO3-xBiAlO3

Antiferroelectric (AFE) materials are potentially useful for energy storage applications. Lead hafnate (PbHfO3) is one of the prototypical AFE materials. However, its critical field (Ecr) which is needed to induce the AFE to ferroelectric phase transition is close to the dielectric breakdown strength. To reduce Ecr, we prepare the solid solutions of (1-x)PbHfO3–xBiAlO3 (x = 0.00–0.04) via solid state synthesis. The crystal structures, dielectric behaviour, ferroelectric properties, and energy storage properties are investigated. A temperature-composition phase diagram is established. At room temperature, the crystal symmetry of all compositions is orthorhombic with the Pbam space group. Upon heating, the transition to the AFE orthorhombic Imma phase is observed at the temperature TC1, which slightly decreases with increasing x, followed by the transition to the cubic phase at the temperature TC2, which does not depend on x. Distinct dielectric anomalies are observed at TC1 and TC2. It is found that BiAlO3 substitution reduces Ecr and the polarization–electric field relations display characteristic double hysteresis loops. For x = 0.04, at a comparatively small applied field of 130 kV/cm, the values of recoverable energy density (Wrec) and efficiency of 0.24 J/cm3 and 84 %, respectively, are obtained. At 190 °C, a Wrec = 0.75 J/cm3 and a very high efficiency of 92 % are obtained at the field of 50 kV/cm. Thus, the prepared material can potentially be used in high-temperature pulsed power capacitors for energy storage applications within the temperature range from room temperature up to 190 °C.

Large electrocaloric effect near room temperature induced by domain switching in ferroelectric nanocomposites

The solid-state refrigeration technique based on the electrocaloric effect (ECE) of ferroelectric materials has been regarded as a promising alternative to vapor compression systems due to its advantages of high efficiency and easy miniaturization. However, the small adiabatic temperature change (ATC) and narrow operating temperature range of ferroelectric materials are key obstacles for their practical applications of ECE refrigeration. To improve the ECE performance of ferroelectric polymer poly(vinylidene fluoride) [P(VDF-TrFE)], PbZr1−xTixO3 (PZT) nanoparticles with larger polarization is herein introduced to form ferroelectric nanocomposites. The phase-field simulation is employed to investigate the dynamic hysteresis loops and corresponding domain evolution of the ferroelectric nanocomposites. The temperature-dependent ATC values are calculated using the indirect method based on the Maxwell relation. The appearance of the double hysteresis loop is observed in P(VDF-TrFE) nanocomposite filled with PbZr0.1Ti0.9O3 nanoparticles [P(VDF-TrFE)–PZT0.9], which is mainly caused by a microscopic domain transition from single domain to polar vortex. Compared to the P(VDF-TrFE), enhanced ATC values associated with the domain transition are unveiled in P(VDF-TrFE)–PZT0.9, and the temperature range of excellent ECE is also effectively broadened. In addition, as the component x of filled PZT nanoparticles increases to cross the morphotropic phase boundary (MPB), the maximum ATC value shows a significant increase. The results presented in this work not only explain the mechanism of domain transition induced excellent ECE in the P(VDF-TrFE)–PZT nanocomposite, but also stimulate future studies on enhancing ECE of P(VDF-TrFE) by introducing ferroelectric nanofillers.

Ultrahigh Energy Storage Density and Efficiency in Orthorhombic PLZST Antiferroelectric Ceramics via Composition Regulation.

PbZrO3-based antiferroelectric (AFE) ceramic materials have emerged as potential candidates for the next generation of high-energy multilayer ceramic capacitors (MLCCs) because of their distinctive characteristics of double hysteresis loops. The energy storage efficiency of orthorhombic AFE ceramics with ultrahigh storage density is relatively low, which hinders their practical application. In this study, the low efficiency limit of PLZST-based orthorhombic ceramics was overcome by precisely adjusting the Sn4+ content in the (Pb0.95Ca0.02La0.02)(Zr0.99-xSnxTi0.01)O3 AFE ceramics. On one hand, the addition of Sn4+ disrupts the original long-range dipole and improves the rapid response of polarization reversal under the applied voltage. As a result, the difference in electric hysteresis under an electric field is reduced, leading to a significant improvement in energy storage efficiency. On the other hand, increasing the Sn4+ content suppresses the formation of oxygen vacancies, inhibiting grain growth and strengthening grain bonding. This results in ceramics with a high breakdown field strength. Ultimately, the resulting PLCZST ceramics reveal an expressively improved recoverable energy density of 10.2 J cm-3 together with a high energy efficiency of 91.4% under a high applied electric field of 560 kV cm-1. The present study demonstrates the tunability of performance in orthorhombic PLZST AFE ceramics, thereby introducing a ceramic material with exceptional energy storage capabilities for MLCC applications.

Energy storage performance and piezoelectric response of silver niobate antiferroelectric thin film

AgNbO3-based antiferroelectric materials have attracted extensive attention in energy storage due to their double polarization-electric field hysteresis loops, but they always suffer from low breakdown strength (Eb). Films with few defects and small thickness exhibit high breakdown strength, which helps to improve energy storage performance. In the present work, an AgNbO3 film with a small thickness of ∼200 nm is prepared via pulsed laser deposition, which has a dense microstructure and a small average grain size of ∼34.5 nm. The AgNbO3 film displays an antiferroelectric nature, as confirmed by the double polarization-electric field hysteresis loops at room temperature. The room temperature phase structure of the AgNbO3 film determined by the dielectric behaviour is the antiferroelectric M2 phase. Due to the small thickness and fine grain size, a high Eb of 1200 kV/cm is obtained, which boosts a recoverable energy storage density (Wrec) of 9.3 J/cm3 and an energy efficiency (η) of 63.7 % in the AgNbO3 film. In addition, Wrec exhibits good temperature stability at 30–120 °C. The AgNbO3 film shows an obvious piezoelectric response after the electric field-induced antiferroelectric-ferroelectric phase transition as confirmed by piezoresponse force microscopy. These results provide guidance for the development of AgNbO3 antiferroelectric films and devices with good energy storage performance.

Unveiling the role of chemical pressure on antiferroelectricity in NaNbO3-based antiferroelectric ceramics

Chemical pressure is widely applied to antiferroelectrics (AFEs) as a criterion to enhance their antiferroelectricity. However, NaNbO3 (NN)-based ceramic with well-defined double polarization hysteresis (P–E) loops was rarely reported based on this strategy, and the effect of chemical pressure on antiferroelectricity remains to be understood. In this work, the Me cations (Me is Ti, Sn, Zr) with different ionic radii were introduced into the component system 0.76NaNbO3–0.20AgNbO3–0.04CaMeO3 to tune the negative chemical pressure and investigate its effect on antiferroelectricity. The enhancement of negative chemical pressure can effectively stabilize the AFE phase and reduce hysteresis, as revealed by the P–E loops and dielectric properties, which is further confirmed by the change in crystal lattice parameters and in situ Raman spectra. Rietveld refinement of x-ray powder diffraction reveals that the enhanced negative chemical pressure mainly reduces the cation off-centering displacement and [BO6] octahedral tilting angles. As a result, the 0.76NaNbO3–0.20AgNbO3–0.04CaZrO3 exhibits good reversibility of the electric field-induced antiferroelectric–ferroelectric phase transition and well-defined double P–E loops. This work reveals the underlying mechanism of chemical pressure and provides an effective way of discovering new NN-based AFEs.

High energy storage density in NaNbO3 antiferroelectrics with double hysteresis loop

Antiferroelectrics (AFEs) possess great potential for high performance dielectric capacitors, due to their distinct double hysteresis loop with high maximum polarization and low remnant polarization. However, the well-known NaNbO3 lead-free antiferroelectric (AFE) ceramic usually exhibits square-like P–E loop related to the irreversible AFE P phase to ferroelectric (FE) Q phase transition, yielding low recoverable energy storage density (Wrec). Herein, significantly improved Wrec up to 3.3 J/cm3 with good energy storage efficiency (η) of 42.4% was achieved in Na0.7Ag0.3Nb0.7Ta0.3O3 (30Ag30Ta) ceramic with well-defined double P–E loop, by tailoring the A-site electronegativity with Ag+ and B-site polarizability with Ta5+. The Transmission Electron Microscope, Piezoresponse Force Microscope and in-situ Raman spectra results verified a good reversibility between AFE P phase and high-field-induced FE Q phase. The improved stability of AFE P phase, being responsible for the double P–E loop and improved Wrec, was attributed to the decreased octahedral tilting angles and cation displacements. This mechanism was revealed by synchrotron X-ray diffraction and Scanning Transmission Electron microscope. This work provides a good paradigm for achieving double P–E loop and high energy storage density in NaNbO3-based ceramics.

Magnetic, Antiferroelectric-like Behavior and Resistance Switching Properties in BiFeO3-CaMnO3 Polycrystalline Thin Films

The effect of ferromagnetic CaMnO3 (CMO) addition to structural, magnetic, dielectric, and ferroelectric properties of BiFeO3 is presented. X-ray diffraction and Raman investigation allowed the identification of a single pseudocubic perovskite structure. The magnetic measurement showed that the prepared films exhibit a ferromagnetic behavior at a low temperature with both coercive field and remnant magnetization increased with increasing CMO content. However, a deterioration of magnetization was observed at room temperature. Ferroelectric study revealed an antiferroelectric-like behavior with a pinched P–E hysteresis loop for 5% CMO doping BFO, resulting in low remnant polarization and double hysteresis loops. Whereas, high remnant polarization and coercive field with a likely square hysteresis loop are obtained for 10% CMO addition. Furthermore, a bipolar resistive switching behavior with a threshold voltage of about 1.8 V is observed for high doped film that can be linked to the ferroelectric polarization switching.

Relaxor Ferroelectric AgNbO3 Film Fabricated on (110) SrTiO3 Substrates via Pulsed Laser Deposition

AgNbO3-based materials have attracted extensive attention in energy storage due to their double hysteresis loops, but they suffer from low breakdown strength (Eb). AgNbO3 films with few defects and small thickness exhibit high Eb, which helps to improve the energy storage performance. In this work, we successfully prepared AgNbO3 thin films on (110) SrTiO3 substrate using pulsed laser deposition technology. The AgNbO3 film shows good crystalline and relaxor ferroelectric behavior. A high Eb up to 1200 kV/cm is obtained in AgNbO3 film, which contributes to good recoverable energy storage density Wrec up to 10.9 J/cm3 and energy efficiency η of 75.3%. Furthermore, the Wrec remains above 2.9 J/cm3 and the η varies between 72.5% and 82.5% in a wide temperature range of 30–150 °C. This work reveals the great potential of relaxor ferroelectric AgNbO3 film for energy storage.

Superior Energy Storage Performance in Antiferroelectric Epitaxial Thin Films via Structural Heterogeneity and Orientation Control

AbstractDielectric capacitors are desired for electronics and electrical power systems because of their fast charge–discharge speed and high‐power density. Nevertheless, dielectric capacitors typically exhibit lower energy densities in comparison to other energy storage systems like batteries or fuel cells. Among dielectrics, antiferroelectrics have shown great promise for high energy density because of their characteristic double hysteresis loops. However, current antiferroelectric capacitors still face challenges of low efficiency and low breakdown strength due to their large hysteresis, which is harmful to energy efficiency and reliability of the system. Herein, by engineering the nanoscale heterogeneity to mitigate hysteresis and controlling orientation to enhance the polarization, the exceptional energy storage performance of antiferroelectric (Pb0.97La0.02)(Zr0.55Sn0.45)O3 epitaxial thin films is demonstrated. Atomic‐resolution transmission electron microscopy and X‐ray reciprocal space mapping confirm the presence of nanoscale structural heterogeneity, characterized by fragmented antipolar nanodomains. These films exhibit remarkable energy densities, reaching up to ≈84.5 J cm−3, coupled with ultrahigh efficiencies of up to ≈98.5% and superior stability, maintaining efficiencies above 92% across a wide field range of ≈5 MV cm−1. Notably, these findings surpass the capabilities of previously reported dielectric materials, opening new avenues for advanced energy storage applications.

MnO2 doping stabilized antiferroelectric P phase and underlying physical mechanism in NaNbO3-SrTiO3 lead-free ceramics

The incorporation of a few amount of MnO2 into 0.88NaNbO3-0.12SrTiO3 lead-free ceramics was found to effectively stabilize the antiferroelectric orthorhombic P phase before its transition into antiferroelectric orthorhombic R phase, consequently featuring completely reversible electric field-induced antiferroelectric-ferroelectric phase transition. Not only reproducible double polarization hysteresis loops but also repeated sprout-like strain-field curves ensure great application potentials in large-displacement lead-free actuators owing to both large repeatedly-utilized strains of ∼0.33% and low driving field of ∼11 kV/mm. Combined results of XPS, Raman spectroscopy and dielectric properties indicate that the stabilized antiferroelectric P phase was closely related to the reduced B-site cation polarizability and oxygen vacancy concentration, while a slight change in antiferrodistortive degree would discourage the P-R phase transition. These results indicate that ionic doping is an alternative method to alter the antiferroelectric P phase stability of NaNbO3-based lead-free ceramics by synergistically considering the influencing factors of phase and crystal structure stability.

A Compact Model of Double Hysteresis Loop for Antiferroelectric Capacitor

A Compact Model of Double Hysteresis Loop for Antiferroelectric Capacitor