Lead-free Relaxor Ferroelectric Ceramics Research Articles

Innovative Design of BNKT-xSLZT Ceramics: Maximizing the Polarization Difference for Enhanced Energy Storage.

Lead-free relaxor ferroelectric ceramics with outstanding energy-storage (ES) density (Wrec) and high ES efficiency (η) are crucial for advanced pulse-power capacitors. This study introduces a strategic approach to maximizing the polarization difference (ΔP) by inducing a transition from the ferroelectric phase to the ergodic relaxor (ER) phase. By employing this strategy, a series of ceramics, (1 - x)(Bi0.5Na0.4K0.1)TiO3-x(Sr0.85La0.1)(Zr0.5Ti0.5)O3 (BNKT-xSLZT), with varying SLZT content (x = 0.05, 0.10, 0.15, and 0.20), were designed. The addition of SLZT enhances cationic disorder, induces vacancies at A sites, and disrupts long-range ferroelectric order, facilitating the formation of polar nanoregions and enhancing relaxor ferroelectric behavior. Furthermore, a viscous polymer process (VPP) technology is employed to optimize the ceramics' structure, aiming to increase the breakdown strength (Eb) and enhance ΔP. Ultimately, enhanced ES performance is demonstrated in BNKT-0.15SLZTVPP, achieving a remarkable Wrec of 6.85 J/cm3 and η of 84% under 470 kV/cm. This composition demonstrates excellent stability with minimal variations in Wrec (3.0%) and η (4.4%) over the temperature range of 20-110 °C. Additionally, BNKT-0.15SLZTVPP exhibits exceptional pulse charge-discharge properties, featuring a high discharge density of 3.72 J/cm3, a large power density of 164.2 MW/cm3, and a short discharge time (t0.9) of 193 ns under 300 kV/cm. The study validates the practicality of BNKT-0.15SLZTVPP for pulse capacitors and underscores the potential to enhance ES performance through A-site donor doping and VPP technology. This work provides a comprehensive understanding of the interplay among composition, structure, and ES properties in lead-free relaxor dielectric ceramics, laying the groundwork for innovative advancements in the field.

Achieving High Energy Storage Performance in Lead-Free Relaxor Ferroelectric Ceramics of (1-x)Bi0.88Nd0.10Sm0.02FeO3-xBaTiO3

BiFeO3-based lead-free ferroelectrics have attracted great interest in energy storage applications due to their high spontaneous polarisation strength, however, the high residual polarisation strength (Pr) has become a serious obstacle to their practical application. In this work, (1-x)Bi0.88Nd0.10Sm0.02FeO3-xBaTiO3+0.1 wt% MnO2 ceramics were designed by ion doping and solid solution modification strategies, where Sm3+ and Nd3+ promote ionic disorder and reduce leakage current, and the introduction of nano-BaTiO3 induces the crushing of long-range ferroelectric structure into polar nano-regions with enhanced relaxation. As a result, the ceramic is able to maintain a high maximum polarisation intensity while possessing a low residual polarisation.The recoverable energy density (Wrec) of the 0.50BSNF-0.50BT ceramic is as high as 3.61 J/cm3 with an efficiency of 70.11%. In addition, the 0.50BSNF-0.50BT has good thermal stability (Wrec variation <7%) at 25-120°C. In the charge/discharge test, the Wdis was 2.58 J/cm3 and the discharge time was 273 ns. These results indicate that the 0.50BSNF-0.50BT ceramic is an ideal candidate as a material for energy storage applications.

Enhanced relaxation behavior and energy storage properties in (Al0.5Nb0.5)4+ complex ions modified Na0.5Bi0.5TiO3-based ceramics under low electric field

In recent decades, high polarization and low residual polarization lead-free relaxor ferroelectric ceramics have attracted lots of focus due to their great potential in dielectric capacitors for energy storage. In this work, Na0.35Bi0.35Sr0.3Ti(1-x)(Al0.5Nb0.5)xO3 (x = 0.00, 0.01, 0.02, 0.03, 0.04, 0.05) lead-free ceramics have been fabricated by the traditional solid-stated reaction method. By doping (Al0.5Nb0.5)4+ complex ions into 0.7Na0.5Bi0.5TiO3-0.3SrTiO3, pure perovskite phases and reduced grain sizes are obtained. Increasing the AN concentration not only moves the Ts toward the lower temperature, but also keeps the permittivity at a high average value, which shows a good thermal stability of the dielectric properties (εr150°C∼3903 ± 15% in the range of 42–232 °C). Furthermore, Na0.35Bi0.35Sr0.3Ti(1-x)(Al0.5Nb0.5)xO3 presents a reduced residual polarization due to the improved relaxor behavior, and achieves a moderate energy storage property at low electric field of 155 kV/cm (when x = 0.04, Wrec is 1.85 J/cm3, and η is 89.0%). More importantly, the ceramic also possesses great frequency, temperature and cycle stability. Hence, the (Al0.5Nb0.5)4+ modified 0.7Na0.5Bi0.5TiO3-0.3SrTiO3 ceramics have exhibited a potential application in dielectric capacitors for energy storage.

Enhanced dielectric energy storage performance of Na0.5Bi0.5TiO3-LiTaO3-based lead-free relaxor ferroelectric ceramics through domain structural regulation and improved densification

Ceramic materials with relaxor dielectric properties, expressed as (1-x)(0.94Na0.5Bi0.5TiO3-0.06LiTaO3)-xCaTiO3 [(1-x)(NBT-LT)-xCT] with x values of 0.12, 0.15, 0.18, and 0.21, were synthesized through an A-site doping method to enhance energy storage capabilities. The linear dielectric CaTiO3 was chosen as the acceptor additive, and ceramic samples were prepared using conventional solid-phase and molding techniques. A comprehensive investigation evaluated the influence of different CT concentrations on the phase and energy storage/release characteristics of NBT-LT.Optimal performance was notably achieved with a 15% CT doping concentration, resulting in Wrec and η values of 2.16 J/cm³ and 70%, respectively, for a 100 μm thick sample under a 210 kV/cm voltage. When the film was rolled to a 60 μm thickness, the voltage strength increased to 330 kV/cm, leading to enhanced Wrec (5.33 J/cm³) and η (80%). Within the temperature range of 30 °C to 150 °C, only a marginal change in Wrec (less than 10%) was observed. Frequency conversion tests across the 1 Hz to 100 Hz range demonstrated the material's relative stability, with Wrec exhibiting minimal fluctuations. These findings emphasize the outstanding temperature and frequency stability of the material. During discharge, the material displayed a power density of up to 152 MW/cm³, coupled with a discharge time of 0.3 μs, showcasing remarkable pulse discharge capabilities. The experimental results affirm the promising potential of (NBT-LT)-0.15CT lead-free relaxor ferroelectric ceramics for application in commercial capacitors.

Fulfilling X9R specification in CeO2 modified BNBST-based relaxor ferroelectric energy storage ceramic capacitors

Future low-voltage driven capacitor devices are appealed to employ the eco-friendly ceramics featured with high-stable dielectric energy storage capabilities. Herein, the dielectric energy storage properties of (Bi0·5Na0.5)0.65(Ba0·3Sr0.7)0.35(Ti0·98Ce0.02)O3+8 wt% K0·5Na0·5NbO3+x wt% CeO2 (BNBSTCK + Cx) lead-free relaxor ferroelectric ceramics were comprehensively investigated. By maintaining the relaxor ferroelectric phases near room temperature and disrupting the ferroelectric long-range order via CeO2 additive, the EIA X9R specification was fulfilled at the best composition of x = 8 over a wide range of −74∼208 °C with a relatively high dielectric constant εr = 904 and low loss tanδ = 10−3 (@25 °C & 1 kHz). Meanwhile, the good recoverable energy storage density Wrec = 0.77 J/cm3 and high efficiency η = 91.6% were achieved only at a low electric field of 95 kV/cm. Furthermore, these ceramics exhibited exceptional frequency and cycle dependent energy storage stability, which could guide the design ideas of long-life X9R ceramic capacitors suitable for high and low working temperature environments in low-voltage driven energy storage applications.

The enhancement of energy storage performance of BaTiO3–Bi(Mg0·5Ti0.5)O3 Pb-free ceramics via an optimized viscous polymer process route

In this study, the viscous polymer processing (VPP) technique is implemented to optimize the characteristics of bulk (1-x)BaTiO3-xBi(Mg0·5Ti0.5)O3 (BT-xBMT) lead-free relaxor ferroelectric ceramics, with a focus on enhancing the recoverable energy storage density (Wrec), improving breakdown strength resistance (Eb), and increasing storage efficiency (η). The influence of polyvinyl alcohol (PVA) inclusion in the VPP process on the resulting dielectric ceramics is thoroughly investigated, covering rheological, dielectric, and ferroelectric properties. The results reveal that a gradual increase in PVA quantity during the VPP process effectively improves the density of ceramic blanks. However, an excess of PVA leads to void formation in the ceramic blanks post-debinding, hindering the achievement of a dense structure in the final ceramics and causing performance degradation. The resulting BT-0.405BMT-40 wt% PVA ceramic showed excellent storage performance, with Wrec, η, and Eb of 6.55 J/cm3 81.45 %, and 480 kV/cm, respectively. In comparison to bulk BT-0.405BMT ceramics, there is a notable 2.47-fold increase in Wrec and a 1.92-fold increase in Eb, accompanied by a substantial improvement in η. Moreover, the BT-BMT-40 wt% PVA ceramic exhibits favorable temperature stability (30–150 °C), frequency stability (1–50 Hz), and commendable charge/discharge performance.

Energy storage properties and stability in Nd3+/Ta5+ modified 0.6Na0.5Bi0.5TiO3-0.4Sr0.7Bi0.2TiO3 lead-free relaxor ferroelectric ceramics under a low electric field

Due to the prevalence of wearable electronic devices, Lead-free dielectric ceramics with excellent recoverable energy storage density and efficiency at low electric fields are well worth investigating. Moreover, maintaining excellent energy storage performance (ESP) in different environments is a huge challenge for researchers. In this study, 0.6Na0·5Bi0·5TiO3-0.4Sr0·7Bi0·2TiO3 lead-free relaxor ferroelectric ceramics were modified by (Sr0.7Nd0.2) (Ta0·4Ti0.5)O3 (BNST-xSNTT x = 0, 0.02, 0.04, 0.06). On one hand, BNT has a very high polarization strength, making it a very suitable basic element for designing high energy storage dielectric materials. On the other hand, Sr0·7Bi0·2TiO3 and (Sr0.7Nd0.2) (Ta0·4Ti0.5)O3 were introduced to improve the performance of ceramics, such as inducing polar nanoregions (PNRs), refining grain size, and increasing impedance. The results demonstrate that the energy storage characteristics of BNST-xSNTT were enhanced by introducing SNTT to the BNST. The ceramics exhibited a significant grain size reduction from 0.946 μm (x = 0) to 0.346 μm (x = 0.06). In addition, a great polarization difference (ΔP = 44.29 μC/cm2) was simultaneously achieved in the x = 0.02 sample. As a result, BNST-2SNTT (x = 0.02) ceramic obtained an excellent recoverable energy density of 3.24 J/cm3 and a satisfactory efficiency of 81.4 % at a low electric field of 190 kV/cm. Furthermore, the BNST-2SNTT ceramic exhibits excellent temperature stability (20°C–140 °C), frequency stability (1 Hz–500 Hz), and cycling reliability (10°-106 cycles). The corresponding fluctuation of ESP is less than 5 %. These properties indicate that the BNST-2SNTT ceramic is an excellent dielectric material for energy storage.

Enhanced energy storage properties in BNST-based lead-free relaxor ferroelectric ceramics achieved via a high-entropy strategy

The 0.65(Bi0.5Na0.5)TiO3–0.35SrTiO3-based materials are essential for the development of pulse power capacitors. However, their low recoverable energy storage density and breakdown field strength have hindered further improvement. To address this, a high-entropy strategy based on multiscale regulation is proposed, which involves synergistically manipulating the activation energy and microstructure evolution in BNST-based ceramics through the introduction of Ba(Zr0.2Ti0.2Sn0.2Hf0.2Ta0.2)O3. The inclusion of high-insulating oxides can significantly raise the activation energy of the entire system. Furthermore, the high-entropy material can significantly increase the atomic disorder and lattice distortion, resulting in strong local polar fluctuations on several nanoscales and excellent energy storage characteristics. As a result, this approach yields an impressive Wrec of ∼ 4.89 J/cm3 and a high efficiency of ∼92.1 % at 351 kV/cm, and the outstanding thermal endurance (20∼150 °C), frequency stability (5∼1000 Hz) and fatigue (100∼105 cycles). This study provides an effective strategy for achieving excellent comprehensive performances in high-entropy ceramics.

BaTiO3-based lead-free relaxor ferroelectric ceramics for high energy storage

Barium titanate (BaTiO3, BT) is widely used in capacitors because of its excellent dielectric properties. However, owing to its high remanent polarisation (Pr) and low dielectric breakdown field strength (Eb), achievement of high energy storage performance is challenging. Herein, a systematic strategy was proposed to reduce Pr and elevate Eb of BT via: (i) modification of the relaxor behavior by alloying it with Bi(Mg2/3Ta1/3)O3 (BMT) and (ii) heightening Eb by introducing NaTaO3 (NT) with high band gap. Consequently, the energy storage efficiency (η) of 90 % and high Eb of 780 kV cm−1 were achieved simultaneously for the BT-BMT-xNT system, which facilitated the recoverable energy density (Wrec) of 6.02 J cm−3. At 300 kV cm−1, its temperature (20–120 °C) and frequency (1–500 Hz) stabilities were found to be good. Moreover, the BT-BMT-0.15NT possessed ultrafast discharge rate (t0.9 < 51 ns) and ultrahigh power density (PD > 94 MW cm−3). This study offers an effective strategy for the design of novel high-performance dielectric energy storage materials.

Temperature stability lock of high-performance lead-free relaxor ferroelectric ceramics

Lead-free dielectric ceramics are considered a highly promising material for pulse power capacitors due to their excellent energy storage performance. However, it is challenging to achieve high-temperature energy storage performance of dielectric ceramics to meet the needs of practical applications. Here, an effective strategy for constructing temperature stability lock is designed to regulate the phase composition and temperature stability based on the polymorphic polarization structure. By realizing the ergodic-state-dominated metastable relaxation structure, high energy storage performance and temperature-insensitive structure can be achieved in relaxor ferroelectric ceramics. Taking the Bi0.5Na0.5TiO3-based solid solution as an example, we demonstrate the metastable relaxation structure induced by the proportion of phase composition. This leads to a large recoverable energy density (Wrec) of 10.7 J cm−3 and a high efficiency (η) of 91 %. Together with the good thermal stability of Wrec (7.1 ± 0.1 J cm−3) and η (86 ± 5 %) values at 500 kV cm−1 in the temperature range from 20 °C to 200 °C, outperforming all reported Bi0.5Na0.5TiO3-based energy storage ceramics. Our work provides a method for obtaining lead-free dielectric ceramics with high-temperature energy storage performance through temperature stability lock.

Enhancement of energy storage performances in BaTiO3-based ceramics via introducing Bi(Mg2/3Sb1/3)O3

Lead-free relaxor ferroelectric ceramics have attracted extensive attention on account of their excellent energy storage properties. However, these ceramics still have some difficulties in improving the energy storage density, efficiency and stability. Herein, (1-x)BaTiO3-xBi(Mg2/3Sb1/3)O3 (BT-xBMS, x = 0.08, 0.12, 0.16, and 0.20) ceramics were designed in this study. After the addition of Bi/Mg/Sb (BMS) elements into BaTiO3(BT) system, the grain size of ceramics increases obviously. And the grain boundary activation energy increases with the increase of resistivity, which is due to the difficulty of grain boundary oxygen vacancy transition. This measure can effectively enhances the breakdown strength (Eb), thereby improving the energy storage properties. Significantly, it is worth mentioning that BT-0.16BMS ceramics exhibit excellent total energy density (Wtotal = 4.56 J/cm3), large recyclable energy storage density (Wrec = 4.28 J/cm3) and high efficiency (η = 93.70 %) under Eb of 550 kV/cm. In particular, BT-0.16BMS ceramics achieved excellent current density (CD = 1475.58 A/cm2), power density (PD = 177.07 MW/cm3), discharge energy density (Wd = 1.35 J/cm3) and extremely fast discharge time (t0.9 = 27.34 ns). In addition, BT-0.16BMS ceramics have excellent temperature range (20–140 °C) and frequency (1–200 Hz) stability. Therefore, the excellent energy storage properties make BT-0.16BMS ceramics have broad prospects in advanced pulse power capacitors.

Multi-scale domain and microstructure engineering for the high-energy-storage BCZT based lead-free relaxor ferroelectric ceramics

Multi-scale domain and microstructure engineering for the high-energy-storage BCZT based lead-free relaxor ferroelectric ceramics

KNN+Nb2O5 co-modified BNBST-based relaxor ferroelectric ceramics for X8R energy storage capacitors

Environmentally friendly ceramics with high dielectric temperature stability and excellent energy storage properties are desired for next generation low-voltage driven pulsed power supply systems. Herein, (Bi0.5Na0.5)0.65(Ba0.3Sr0.7)0.35(Ti0.98Ce0.02)O3+x wt% K0.5Na0.5NbO3 (KNN) + y wt% Nb2O5 (abbreviated as BNBSTC + KxNy) lead-free relaxor ferroelectric ceramics are prepared to investigate the effect of KNN + Nb2O5 co-modification on the structure and dielectric energy storage properties. In optimized BNBSTC + K8N8 ceramics, a medium high εr = 1310 with low tanδ = 5 × 10−3 (@25 °C & 1 kHz) meeting the EIA X8R standard can be achieved in addition to a recoverable energy storage density Wrec = 0.92 J/cm3 with high efficiency η = 93% only at a low electric field of 100 kV/cm. Moreover, the BNBSTC + K8N8 ceramics exhibits excellent energy storage stability under different frequency, fatigue cycle and temperature testing environments, showing an attractive prospect in low-voltage driven X8R dielectric energy storage capacitors.

Local Heterogeneous Polarization Enhanced Superior Low-Field Energy Storage Performance in Lead-Free Relaxor Ferroelectric Ceramics

Local Heterogeneous Polarization Enhanced Superior Low-Field Energy Storage Performance in Lead-Free Relaxor Ferroelectric Ceramics

Obtaining high breakdown strength and excellent charge–discharge properties in bismuth ferrite-based lead-free relaxor ferroelectric ceramics

Obtaining high breakdown strength and excellent charge–discharge properties in bismuth ferrite-based lead-free relaxor ferroelectric ceramics

Simultaneously achieving high energy storage and charge-discharge performance by Nd-doped Sr0.7Bi0.2TiO3 lead-free relaxor ferroelectric ceramics

Dielectric capacitors have been extensively studied in electronic and power systems based on their high power density and ultra-fast discharge rates. In this study, the dielectric, energy storage and charge-discharge properties of Sr0.7Bi0.2TiO3-based lead-free relaxor ferroelectric ceramic were investigated. The dielectric breakdown strength was significantly improved by introducing the rare earth element Nd, which was attributed to the rise in resistivity and large band gap. The results show that Sr0.7Bi0.15Nd0.05TiO3 obtain a high recoverable energy storage density of 2.34 J/cm3 with high efficiency of 92%. In addition, pulsed charge-discharge tests demonstrated that Sr0.7Bi0.15Nd0.05TiO3 possesses a high power density of 73.5 MW/cm3, a short discharge period of 0.1 μs, and a pulsed discharge energy density of 2.0 J/cm3. Meanwhile, the energy storage performance of Sr0.7Bi0.15Nd0.05TiO3 exhibits excellent stability of temperature, frequency and cycling. This work provides a systematic study and a new strategy for enhancing the performance of SBT ceramics.

Enhanced DC-biased energy-storage performance in lead-free relaxor ferroelectric ceramics for high-density power converters

Dielectric energy-storage capacitors are among the main enabling technologies in high-density power converters, in which lead-free relaxor ferroelectric ceramics have been paid particular attention to. However, low energy-storage performance at elevated temperature and high electric field, and the lack of application-oriented evaluation are among the primary blocks stumbling their progress. As a demonstration, 0.87BaTiO3-0.13Bi[Zn2/3(Nb0.85Ta0.15)1/3]O3 (BTBZNT) lead-free relaxor ferroelectric ceramics were modified by linear dielectric CaZrO3 (CZ) with various contents of 0, 0.1, 0.2, and 0.3 (CZ0, CZ1, CZ2, and CZ3). XRD and Raman results reveal major perovskite phases, and densely sintered ceramics were witnessed from the SEM images. Unchanged weakly coupled relaxor behavior was confirmed by the big critical coefficient of 1.6–1.8 from the modified Curie–Weiss law and the large activation energy of 0.29–0.32 eV from the Volgel–Fulcher fittings, and CZ was found to suppress high-temperature loss. From the normal polarization–electric field (P–E) loops, CZ0 is optimal for energy-storage owing to the highest discharged energy density and modest efficiency. Nevertheless, from the application-oriented DC-biased P–E loops, CZ1 is oppositely superior to CZ0 because of the higher permittivity and lower loss leading to higher discharged energy density and efficiency at DC-biased electric field. Moreover, CZ1 outperforms CZ0 in the higher capacitance density and lower temperature rise at higher temperature and electric field. Enhanced DC-biased energy-storage performance in BTBZNT ceramics modified by CZ was achieved, which should enlighten the advance of energy-storage ceramics targeting the application in high-density power converters.

Improved energy storage performance in rare-earth modified lead-free BNT-based relaxor ferroelectric ceramics

Dielectric ceramic capacitors with high energy storage performance are indispensable components in high-power pulse electronic systems. Herein, a collaborative optimization design is employed to achieve excellent energy storage performance in rare-earth oxides modified 0.76(0.94Bi0.5Na0.5TiO3-0.06BaTiO3)-0.24Sr0.7Bi0.2TiO3 (BNBT-SBT) ceramics by simultaneously enhancing the breakdown field strength (Eb) and relaxor behavior. To this end, ferroelectric domains are partially transformed into polar nanoregions by introducing relaxor ferroelectric SBT, while a smaller grain size is produced by doping rare-earth elements to improve the Eb and further disrupt the long-range order of ferroelectric polarization. It is found that the La-doped BNBT-SBT ceramic simultaneously exhibits a superior energy storage density of 4.4 J cm−3 and an ultrahigh efficiency of ∼91% under a moderate electric field of 300 kV/cm. The good temperature stability (30–120 °C), frequency endurance (1–100 Hz), electric fatigue resistance (1–106 cycles), and excellent power density (108 MW cm−3) are also obtained in the lead-free Bi0.5Na0.5TiO3-based relaxor ferroelectric ceramics. These prominent properties indicate that the La-doped BNBT-SBT ceramic is a promising candidate for applications of high-energy storage capacitors.

Simultaneously realizing ultrahigh energy storage density and efficiency in BaTiO3-based dielectric ceramics by creating highly dynamic polar nanoregions and intrinsic conduction

Nowadays, it is urgent to explore advanced and eco-friendly energy storage capacitors based on lead-free relaxor ferroelectric (RFE) ceramics in order to meet the ever-increasing requirements in pulsed power systems. BaTiO3 (BT)-based RFE ceramics are considered as ones of the best high-temperature energy storage materials due to their good thermal stability. However, relatively low recoverable energy storage density (Wrec<5 J/cm3) has been a key bottleneck restricting the practical applications of them. Here, a novel strategy is proposed to create highly dynamic PNRs and the intrinsic conduction by introducing Bi(M1-0.015xTa0.015x)O3+0.015x (BMO-Ta, M=Mg2/3Ta1/3) to BT matrix. As a consequence, the designed (1-x)BT-x(BMO-Ta) ceramics exhibit dramatically enhanced energy storage properties including ultrahigh Wrec and efficiency (η), because of the coexistence of very slim polarization hysteresis (P-E) loops, large polarization difference (ΔP) and giant dielectric breakdown electric strength (Eb). Wrec and η of the x=0.25 ceramic reach up to 9.03 J/cm3 and 95.2% under 720 kV/cm, respectively. Furthermore, it shows excellent temperature/frequency/cycling stability over a wide range of 20−200 °C, 1−500 Hz and 1−3.3 × 105 cycles, respectively (the variations of Wrec and η are < 3% and < 4%, respectively). The findings in this paper not only indicate excellent comprehensive properties achieved in the novel (1-x)BT-x(BMO-Ta) system, but also provide an effective approach to explore advanced energy storage capacitors in other lead-free ceramic systems.

BaTiO3-Bi(Mg3/4W1/4)O3 lead-free relaxor ferroelectric ceramics with improved energy storage properties

BaTiO3-Bi(Mg3/4W1/4)O3 lead-free relaxor ferroelectric ceramics with improved energy storage properties