Fabrication,structural and dielectric property of lead-free perovskite silver niobate ceramics

Dielectric capacitors with high recoverable energy density are in high demand for their application in electrical and electronic systems. Among lead-free dielectric materials, silver niobate (AgNbO₃) has attracted growing interest due to its superior energy storage density at room temperature. The field-induced phase transition from antiferroelectric (AFE) phase to ferroelectric (FE) phase contributes to its large energy density. In this work, pure perovskite silver niobate ceramics were fabricated in an oxygen atmosphere by the solid-state reaction technique. The Pbcm orthorhombic phase of AgNbO₃ was closely observed using the Rietveld refinement method to provide explanation for the origin of high spontaneous polarization within a unit cell. Local structural analysis via piezoelectric force microscopy revealed the existence of ferroelectric nano domains, which may contribute to the high energy storage efficiency (η = 99.9926%) in AgNbO₃ at low electric fields. The phase transitions of AgNbO₃ were also investigated via the dependence of the dielectric permittivity (ε′ and ε″) and loss angle tangent (tanδ) on temperatures, providing insights into the further modification of AgNbO₃.     

High energy-storage performance of lead-free AgNbO3 antiferroelectric ceramics fabricated via a facile approach

AgNbO₃ lead free AFE ceramics are considered as one of the promising alternatives to energy storage applications. In the majority of studies concerning the preparation of AgNbO₃ AFE ceramics, an oxygen atmosphere is required to achieve high performance, increasing the complexity of the fabrication process. Herein, a facile approach to preparing AgNbO₃ ceramics in the ambient air was reported, in which the AgNbO₃ ultrafine powder with stable perovskite structure was synthesized by hydrothermal method instead of the conventional ball milling process, leading to a lower temperature of phase formation and thus smaller grain size. The resulting ceramics sintered at 940 °C displayed high breakdown strength (216 kV/cm) and a recoverable energy density of 3.26 J/cm³ with efficiency of 53.5 %. Also, the high thermal stability of recoverable energy density (with minimal variation of ≤20 %) and efficiency (≤ 10 %) over 30–150℃, enables AgNbO₃ ceramics achieved to be a promising candidate for energy storage applications.     

Preparation and optimization of silver niobate-based lead-free ceramic energy storage materials

AgNbO₃ has broad research prospects in dielectric energy storage due to its unique antiferroelectric properties. The enhancement of ferroelectric/antiferroelectric phase stability can be achieved by tuning the tolerance factor t of AgNbO₃-based ceramics. On the other hand, the stability of the antiferroelectric and ferroelectric phases can be improved by adjusting the phase transition temperature of AgNbO₃-based ceramics. This is of great significance and value to the research and development of lead-free energy storage materials. Although there have been many studies on the energy storage performance of AgNbO₃-based ceramic materials, there are still challenges in achieving high energy storage density and energy efficiency at the same time. This review discusses the optimization strategy, preparation technology, and sintering technology of AgNbO3-based ceramics, summarizes the current research progress and obstacles, and puts forward the development direction for the application of AgNbO₃-based ceramics.     

High-performance antiferroelectric ceramics via multistage phase transition

Lead-based antiferroelectric (AFE) ceramics have attracted increasing interest in pulse power systems owing to their high-energy storage and power densities. However, the single AFE–ferroelectric (FE) phase transition in conventional AFE materials usually leads to premature polarization saturation and low breakdown strength, which are disadvantageous to energy storage performance. In this study, high energy storage performance was achieved in Pb_0.94−xLa_0.04Ca_x[Nb_0.02(Zr_0.99Ti_0.01)_0.975]O₃ (PLCNZT) AFE ceramics by constructing electric-field-induced multiple phase transitions. A maximum recoverable energy storage density of 12.15 J/cm³ and a high energy efficiency of 85.4% were obtained for the PLCNZT ceramic with x = 0.03 at 420 kV/cm. These excellent properties are attributed to the AFE–FE Ⅰ-FE Ⅱ multiple phase transitions induced by Ca²⁺ doping, which effectively enhances the breakdown strength. This result indicates that field-induced multiple phase transitions significantly improve the energy storage of AFE materials.     

Structure and energy storage performance of Ba-modified AgNbO3 lead-free antiferroelectric ceramics

The AgNbO₃ antiferroelectric (AFE) ceramics have attracted increasing attention for their high energy storage performance and environmentally friendly characters. In this work, Ag_1–2xBa_xNbO₃ ceramics were successfully prepared by the conventional solid-state reaction method. The effect of Ba-modification on phase structure, microstructure, and electric properties was systematically investigated. The introduction of Ba²⁺ ion led to complex cell parameter evolution and significant refinement of grain size. Room temperature dielectric permittivity increased obviously from ~260 for the pure AgNbO₃ counterpart to ~350 for those after adding a small amount of Ba element. Slim P-E hysteresis loops with improved AFE phase were achieved after Ba modification, due to the decrease of tolerance factor. A high recoverable energy density up to 2.3?J/cm³ with energy efficiency of 46% can be obtained for the composition of Ag_0.96Ba_0.02NbO₃, in correlation with the enhanced AFE stability, reduced P_r, increased P_m and decreased ΔE. Moreover, the Ag_0.96Ba_0.02NbO₃ ceramics also exhibited excellent temperature stability in both energy density and efficiency with small variation of <?5% over 20–120?℃. The results suggest that the electric properties of AgNbO₃ system can be largely tuned after Ba modification, making it a promising candidate for energy storage applications.     

Dielectric and ferroelectric properties of lanthanum‐modified lead zirconate stannate titanate (42/40/18) ceramics

The effect of lanthanum (La) content on the phase transformation of Pb_1?3x/2La_x(Zr_0.42Sn_0.40Ti_0.18)O₃ (PLZST 100x/42/40/18, 0 ≤ x ≤ 0.06) ceramics was investigated by the dielectric and ferroelectric properties. The base composition PLZST 0/42/40/18 located in the ferroelectric (FE) rhombohedral phase region. As x increased, the compositions showed successively FE and antiferroelectric (AFE) state at room temperature, and their peak temperatures (T_max) decreased gradually in line as T_max = 162.21‐1507x. Evidence was presented that there were two dielectric anomalies in PLZST 2/42/40/18, which were corresponding to the FE‐AFE and AFE‐paraelectric (PE) phase transformations, respectively. With increasing the dc bias fields, the two phases merged into one. PLZST 3/42/40/18 showed AFE characteristics with the first loop outside of the second loop and there was only one dielectric inflection. The critical lanthanum content occurred at x = 0.03 from the dielectric temperature spectra and hysteresis loops. Furthermore increase in La above 0.03, these compositions showed typical antiferroelectric behaviors with double hysteresis loops. The stored energy properties of the three compositions (PLZST 4/42/40/18, 5/42/40/18 and 6/42/40/18) displayed different temperature dependencies from room temperature to 140°C (over their respective T_max). Comparing the above results with previous investigations on PLZSTs, some questions were discussed.     

Enhanced energy storage density in Ca and Ta co-doped AgNbO3 antiferroelectric ceramics

Ca and Ta co-doped AgNbO₃ antiferroelectric lead-free ceramics were fabricated by rolling process technique, and improved energy storage properties were obtained. X-ray diffraction and Raman spectra indicate a single perovskite structure for (Ag_1-2xCa_x)(Nb_1-xTa_x)O₃ ceramics. The dielectric performances were also investigated, showing that increasing the content of Ca and Ta from 0.1 to 5 mol% gradually decreased the temperatures of the phase transition of monoclinic M₁-M₂ and M₂-M₃. This proved the enhanced antiferroelectricity stability associated with the enlarged low temperature phase transition region. The obtained (Ag_0.90Ca_0.05)(Nb_0.95Ta_0.05)O₃ ceramics exhibit an enhanced recoverable energy storage density (3.36 J/cm³) and efficiency (58.3%) with good temperature and frequency stability. The same composition shows excellent charge and discharge properties with a discharge current as high as 91.5 A and fast discharge speed (150 ns discharge period). All these merits demonstrate that AgNbO₃-based antiferroelectric ceramics are competitive with other lead-based and lead-free dielectric capacitors, which are promising candidates for dielectric energy storage applications.     

High‐Energy Storage Performance of (Pb0.87Ba0.1La0.02)(Zr0.68Sn0.24Ti0.08)O3 Antiferroelectric Ceramics Fabricated by the Hot‐Press Sintering Method

(Pb_0.87Ba_0.1La_0.02)(Zr_0.68Sn_0.24Ti_0.08)O₃ (PBLZST) antiferroelectric (AFE) ceramics have been prepared by hot‐press sintering method and conventional solid‐state reaction process, and the dependence of microstructure and energy storage properties of the ceramics on sintering approaches has been studied. The results reveal that not only the microstructure, but also the electrical properties of the PBLZST AFE ceramics are significantly improved by using the hot‐press sintering method. Samples resulting from the hot‐press sintering process have high breakdown strength of 180 kV/cm which results from the increase of density. Coupled with large polarization, the hot‐pressed AFE ceramics are shown to have a high recoverable energy density of 3.2 J/cm³. The recoverable energy density of the hot‐pressed PBLZST AFE ceramics is 100% greater than the conventional sintered specimens with recoverable energy density of 1.6 J/cm³.     

High‐Energy Storage Performance in (Pb0.98La0.02)(Zr0.45Sn0.55)0.995O3 AFE Thick Films Fabricated via a Rolling Process

(Pb_0.98La_0.02)(Zr_0.45Sn_0.55)_0.995O₃ antiferroelectric (AFE) thick films with a thickness of about 85 μm were successfully fabricated via a rolling process using an improved sintering method, and all specimens showed high‐energy‐storage performance. The X‐ray diffraction, SEM pictures, and hysteresis loops confirmed that the sintering temperature had an important influence on the microstructures, dielectric properties and energy storage performance of AFE thick films. The grain size and the storage efficiency increased with the increasing sintering temperature, the energy storage performance was enlarged by the rolling process. As a result, a maximum recoverable energy density of 7.09 J/cm³ with an efficiency of 88% was achieved at room temperature, together with stable energy‐storage behavior, which was almost three times higher than that (2.43 J/cm³) of the bulk ceramics counterparts. The results demonstrated that the improved method was an effective way to improve the breakdown strength and energy storage performance of AFE thick films, and (Pb_0.98La_0.02)(Zr_0.45Sn_0.55)_0.995O₃ AFE thick films were a promising material for high‐power energy storage.     

Phase transition behavior of Pb(Hf,Sn, Ti,Nb)O3 ceramics at morphotropic phase boundary

The phase transition and dielectric properties of Pb_0.988(Hf_0.945Sn_xTi_0.03-xNb_0.025)O₃ ceramics (0 ≤ x ≤ 0.03, correspondingly abbreviated as H1, H2, H3, and H4) at the morphotropic phase boundary were systematically investigated. X-ray diffraction results and P-E hysteresis loops show that the dominate orthorhombic antiferroelectric phase and a small amount of the tetragonal FE phase coexist in Pb_0.988(Hf_0.945Sn_xTi_0.03-xNb_0.025)O₃ ceramics. As the Sn content increases, the antiferroelectricity is significantly enhanced, accompanied with an increased Curie temperature and sharply reduced peak dielectric constant. H1 and H2 experience an irreversible field-induced AFE-FE phase transition at the ambient temperature, and the transition from a metastable FE phase to the original AFE phase is observed in H2 when heated to 60°C. H3 and H4 experience an invertible AFE-FE phase transition, along with an enhanced forward phase switching field E_F. Moreover a decreased backward phase switching field E_A for H4 is detected as the electric field increases due to the AFE/FE coexistence. These results reveal the unique phase transition characteristics of AFE materials near the phase boundary, which is helpful for better understanding of AFE/FE materials.     

Phase transition and energy storage behavior of antiferroelectric PLZT thin films epitaxially deposited on SRO buffered STO single crystal substrates

(Pb_0.98, La_0.02)(Zr_0.95, Ti_0.05)O₃ (PLZT) thin films of 300 nm thickness were epitaxially deposited on (100), (110), and (111) SrTiO₃ single crystal substrates by pulsed laser deposition. X-ray diffraction line and reciprocal space mapping scans were used to determine the crystal structure. Tetragonal ((001) PLZT) and monoclinic M_A ((011) and (111) PLZT) structures were found, which influenced the stored energy density. Electric field-induced antiferroelectric to ferroelectric (AFE→FE) phase transitions were found to have a large reversible energy density of up to 30 J/cm³. With increasing temperature, an AFE to relaxor ferroelectric (AFE→RFE) transition was found. The RFE phase exhibited lower energy loss, and an improved energy storage efficiency. The results are discussed from the perspective of crystal structure, dielectric phase transitions, and energy storage characteristics. Besides, unipolar drive was also performed, providing notably higher energy storage efficiency values due to low energy losses.     

Revealing the solid-state processing mechanisms of antiferroelectric AgNbO3 for energy storage

AgNbO₃ is one of the prominent lead-free antiferroelectric (AFE) oxides, which readily exhibits a field-induced AFE to ferroelectric phase transition and thus a high energy storage density. The solid-state synthesis of AgNbO₃ is considered difficult and an oxidizing atmosphere is typically employed during AgNbO₃ processing, on the premise that oxygen can prevent possible decomposition of the silver oxide at high temperatures. However, details about the influence of processing parameters on the functional properties of AFE AgNbO₃ are insufficiently understood. In this work, the solid-state reaction of a stoichiometric AgO and Nb₂O₅ mixture was investigated. We found that ball milling can convert AgO into metallic Ag, which is beneficial for lowering the reaction temperature for the formation of the perovskite phase to 500‒600℃. Moreover, the influence of the processing atmosphere (air, O₂, and N₂) was investigated by thermal analysis and in situ X-ray diffraction. Since the reaction between Ag and Nb₂O₅ to form AgNbO₃ requires oxygen uptake, AgNbO₃ was only found to form in air and O₂, whereby the kinetics were faster in the latter case. All the sintered AgNbO₃ samples exhibited a similar crystallographic structure, although the samples processed in O₂ had a lower oxygen vacancy concentration. Despite this, well-defined AFE double polarization loops were obtained in all cases. Our results indicate that decomposition of sliver oxide during ball milling is beneficial for the solid-state reaction, while a pure O₂ atmosphere is not essential for the synthesis of high-quality AgNbO₃. These findings may simplify the processing and facilitate further research of AgNbO₃-based antiferroelectrics.     

Temperature‐stable dielectric and energy storage properties of La(Ti0.5Mg0.5)O3‐doped (Bi0.5Na0.5)TiO3‐(Sr0.7Bi0.2)TiO3 lead‐free ceramics

A new type of (0.7?x)Bi_0.5Na_0.5TiO₃‐0.3Sr_0.7Bi_0.2TiO₃‐xLaTi_0.5Mg_0.5O₃ (LTM1000x, x = 0.0, 0.005, 0.01, 0.03, 0.05 wt%) lead‐free energy storage ceramic material was prepared by a combining ternary perovskite compounds, and the phase transition, dielectric, and energy storage characteristics were analyzed. It was found that the ceramic materials can achieve a stable dielectric property with a large dielectric constant in a wide temperature range with proper doping. The dielectric constant was stable at 2170 ± 15% in the temperature range of 35‐363°C at LTM05. In addition, the storage energy density was greatly improved to 1.32 J/cm³ with a high‐energy storage efficiency of 75% at the composition. More importantly, the energy storage density exhibited good temperature stability in the measurement range, which was maintained within 5% in the temperature range of 30‐110°C. Particularly, LTM05 show excellent fatigue resistance within 10⁶ fatigue cycles. The results show that the ceramic material is a promising material for temperature‐stable energy storage.     

Li+ and Sm3+ co-doped AgNbO3-based antiferroelectric ceramics for high-power energy storage

Ag_1-x-3yLi_xSm_yNbO₃ (x≤0.05, y≤0.05) (ALSN) antiferroelectric ceramics were successfully prepared via conventional solid-state reaction and sinter routes in oxygen atmosphere for improving the energy storage characteristic of pure AgNbO₃. The results indicate that all of the studied compositions display a pure orthorhombic antiferroelectric (AFE) perovskite structure, while their key parameters of electric-field-induced antiferroelectric-ferroelectric transition can be affected by Li⁺ or/and Sm³⁺ doping contents. The Sm³⁺ doping can enhance the stability of antiferroelectric state, giving rise to higher antiferroelectric-ferroelectric transition electric-field (E_F and E_B), while Li⁺ doping can reduce E_F and E_B for Sm³⁺ doped AgNbO₃ with low Sm³⁺ content (y≤0.03). When co-doping the same amounts of Li⁺ and Sm³⁺ at x=y≤0.03, both E_F and E_B almost remain unchanged. At x=y=0.05, the diffuse phase transition (DPT) behavior of antiferroelectric-paraelectric (AFE-PE) phase transition occurred, resulting in a “slim-like” double-polarization hysteresis with significantly enhanced E_F. Due to these features, both W_rec and η are improved compared with pure AgNbO₃. The W_rec and η with composition at x=y=0.05 is 2.33 J/cm³ and 58% under applying electric field of 240 kV/cm, respectively. The results suggest that building DPT behavior of AFE-PE phase transition could be an alternative strategy to improve the energy storage characteristic of AgNbO₃.     

Achieving high energy storage performance of Pb(Lu1/2Nb1/2)O3 antiferroelectric ceramics via equivalent A-site engineering

Manipulating the critical switching field between antiferroelectric (AFE) state and ferroelectric (FE) is an important concept for tuning the energy storage performance of AFEs. As one of the lead-based AFE systems, Pb(Lu_1/2Nb_1/2)O₃ promises high potential in the miniaturization of pulsed power capacitors, but the extremely high critical switching field and low induced saturated polarization demonstrate severe drawbacks with respect to temperature stability and flexibility. Here, A-site Ba²⁺ doping engineering is used to effectively reduce the critical switching field and improve the saturated polarization in Ba_xPb_1-x(Lu_1/2Nb_1/2)O₃ (0.01 ≤ x ≤ 0.08, abbreviated as xBa-PLN) ceramics. We found the AFE-FE phase transition can be occurred at 80ºC with a high energy storage density of 4.03 J/cm³ for Ba_0.06Pb_0.94(Lu_1/2Nb_1/2)O₃ ceramic. Our results show that Ba²⁺ additions destroy the antiparallel structure of AFE phase, and finally reduce the critical switching field, demonstrating a potential alternative to modulate the energy storage performance of AFEs.     

Influence of Crystallization Temperature on Ferroelectric Properties of Na0.9K0.1NbO3 Glass‐Ceramics

The correlation between the crystallization temperature and ferroelectric properties is studied by the measurements of impedance spectroscopy, activation energy, dielectric breakdown strength and dielectric constant in Na_0.9K_0.1NbO₃ glass‐ceramics, while different nucleating agents are added to optimize performance. It is found that the glass‐ceramics crystallized at the temperatures of the second exothermic peak (about 900°C) have higher crystal degree, lager interface numbers and larger amount of bulk charges accumulated at the interfaces. However, the higher crystal degree of ferroelectric phase results in a lower value of resistivity and E_a which represent better charge spreading behavior. The better charge spreading behavior and drastic increase in the accumulation of bulk charge also result in low breakdown strength. The results show that the glass‐ceramics heated at the temperature of first exothermic peak (about 700°C) with a reasonable crystal degree obtain higher energy storage density which is 1.94 J/cm³.     

Low‐Temperature Magnetic and Dielectric Anomalies in Rare‐Earth‐Substituted BiFeO3 Ceramics

In this work, we report on the magnetic and dielectric anomalies observed in dense Bi_1–xRE_xFeO₃ ceramics (RE = Dy, Tb; 0 ≤ x ≤ 0.3) at cryogenic temperatures. For compositions with a high content of rare‐earth ions, thermomagnetic experiments revealed a distinct anomaly in the magnetization curves at temperatures below 200 K. The temperature of the magnetic anomaly along with a thermal hysteresis was found to be dependent on the rare‐earth concentration and magnetic field strength. Low‐temperature dielectric measurements showed an anomalous relaxor‐like behavior of the relative permittivity and dielectric loss in highly doped ceramic samples. The anomalies in low‐temperature magnetization and dielectric response are suggested to result from the presence of GdFeO₃‐like orthoferrite phase and/or bismuth rare‐earth‐mixed iron garnet impurities.     

Synergic modulation of over-stoichiometrical MnO2 and SiO2-coated particles on the energy storage properties of silver niobate-based ceramics

AgNbO₃-based ceramics have been the spotlight for the lead-free dielectric capacitors due to its unique antiferroelectric feature and the ever-increasing environmental concerns. Herein, synergic modulation on the energy storage properties of AgNbO₃-based ceramics was reported, in which the over-stoichiometrical introduction of only 0.10 wt% MnO₂ at the atomic-scale leads to reduced leakage current, P_r and enhanced antiferroelectric stability while the SiO₂ coating on the AgNbO₃ particles at the micro-scale greatly inhibits the grain growth, increases the breakdown strength and the electric filed inducing the AFE-FE transitions. As a result, a large recoverable energy density up to 3.34 J/cm³ with efficiency of 60.0% was obtained in 0.10 wt% MnO₂-doped AgNbO₃@SiO₂ ceramic, which is 2.3 times larger than that of the pristine AgNbO₃. This work provides a rational approach to synergically modulate the energy storage properties.     

Low‐Temperature Phase Transition in AgNbO3

AgNbO₃ is a weak ferroelectric with antiferroelectricity due to Ag displacements at room temperature. A dielectric anomaly at 250 K, which has not been observed previously, reveals a transition between the weak ferroelectric phase (M1 phase) at the higher temperature and a new ferroelectric phase (M0 phase) at the lower temperature in AgNbO₃. This transition was further verified by the pyroelectric current and differential scanning calorimetry measurements. The spontaneous polarization value is found to be much larger in the M0 phase than that of the M1 phase. A well‐defined saturating ferroelectric hysteresis loop can also be observed at 77 K, showing a remnant polarization value of 2.4 μC/cm² and a coercive field of 25 kV/cm. All the above results indicate that the larger polarization of the M0 phase mainly comes from the alignment of the antiferroelectric displacements of the Ag atoms.     

Diffuse dielectric behaviors in non-stoichiometric sodium niobate-based ceramics via Bi-substitution

Systematic investigation on the phase transition, dielectric behavior, and ferroelectric property of non-stoichiometric sodium niobate-based antiferroelectric (AFE) ceramics is carried out via Bi-substitution. Doping Bi³⁺ is capable of adjusting phase transition temperature meanwhile accelerating the formation of polar nanoregions instead of the long-range order structure. The phase transition is identified by the structural Rietveld refinement from the orthorhombic P phase to the pseudo-cubic phase consisting of the P and orthorhombic R phase as Bi³⁺ dopant increases. The composition regulation shifts the dielectric anomaly to a lower temperature and effectively enhances the relaxor nature. Specifically, associated with the diffuse dielectric relaxation aroused by oxygen vacancy defect, excellent thermal stability is achieved in a wide temperature range from ?82 °C to 408 °C. Additionally, the simultaneously significant improvement of the recoverable energy density and efficiency is gained at moderate electric fields. This work makes it an alternative AFE strategy for the application of high-temperature capacitor.