Energy Storage Ceramics Research Articles

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.

Realizing Ultrahigh Energy Storage Density in (Bi0.5Na0.5)0.94Ba0.06TiO3-Based Ceramics via Manipulating the Domain Configuration and Grain Boundary Density.

Dielectric capacitors with a high power density are widely used in various pulsed power electronic systems. However, their low comprehensive energy storage performance severely limits the development of these systems in terms of miniaturization and lightweight design. Herein, we achieved decent energy storage performance in a class of (Bi0.5Na0.5)0.94Ba0.06TiO3 (BNTBT)-based ceramics by synergistically manipulating domain configurations and grain boundary densities. High-resolution transmission electron microscopy and piezoresponse force microscopy confirm that composition-driven refined domain configurations with weak polarity effectively improve the polarization response of BNTBT-based ceramics. The results of experimental and phase-field simulation analysis indicate that the refined grain size contributes to its high breakdown electric strength (Eb). Benefiting from the high polarization difference (ΔP) of 32.62 μC/cm2, delayed saturation polarization behavior, and an ultrahigh Eb of 815.00 kV/cm, BNT-based ceramics simultaneously achieve a high energy storage density (Wrec) of ∼12.25 J/cm3 and an efficiency (η) of ∼86.90%. Because of these structure-induced advantages, the ceramics also exhibit good energy storage temperature stability in the range of 30-150 °C. We believe that the findings of this work may provide practical guidance for the development of high-performance energy storage ceramics.

Enhanced energy storage performance of tungsten bronze structured BaNb2O6-modified (Bi0.5Na0.5)TiO3 ceramics

The rapid development of the electronic devices and increasing attention to environmental problems have put forward a huge demand for high-performance lead-free dielectric energy storage ceramics. In this work, tungsten bronze structured BaNb2O6 (BN) modified perovskite structured (Bi0.5Na0.5)TiO3 (BNT) ceramics, BNT-xBN (0 <x< 0.15), were prepared to optimize the energy storage performance of BNT. The results show that the lattice distortion and dielectric relaxation behavior of BNT ceramic can be induced by BN addition. Meanwhile, the introduction of tungsten bronze structured BN results in the grain refinement and the increasing of resistivity, thereby significantly enhancing the electrical breakdown strength (Eb). Accordingly, the BNT-0.1BN ceramic displays good energy storage performance with high recoverable energy density (Wrec ∼ 3.41 J/cm3) at an great Eb of 358 kV/cm, accompanied by the wide temperature stability at 30–150 °C (Wrec varies within ±12.8 %, efficiency (η) varies within ±6.7 %). The enhanced energy storage performance demonstrates that introducing tungsten bronze structure is a feasible method to prepare high-performance perovskite energy storage ceramics.

Structure regulation and performance optimization mechanism of Sr0.7Bi0.2TiO3-based energy storage ceramics based on charged defect design engineering

The linear-like relaxor ferroelectric Sr0.7Bi0.2TiO3 with regulable microstructure offers a new platform to reveal the essential mechanism of energy storage properties improvement and develop advanced pulse capacitors. Herein, Li with relatively weak volatility accompanied by Bi was introduced in Sr0.7Bi0.2TiO3 to form a charged defect and increase the maximum polarization (Pmax) while avoiding the deterioration of dielectric breakdown strength (BDS). The occupation of Li and the formation of Li-Bi defect dipole polar were analyzed using first principle calculations. A unique local superlattice induced by the lattice distortion was first observed in related systems. The Pmax was enhanced due to the increased size and number of polar structures. The breakdown behaviour and local electric field distribution were analyzed using numerical simulation. The BDS was improved due to the decreased oxygen vacancies, high thermal conductivity and enhanced electrical insulation. The excellent and stable energy storage performance was achieved in different temperatures, frequencies and cycles. Meanwhile, the optimized sample possesses excellent and stable charge–discharge properties, especially fatigue resistance (105 cycles under 25 °C and 150 °C). After the process optimization, the sample shows a higher energy storage density of 3.44 J/cm3 with a high efficiency of 93.74 % at 345 kV/cm due to the further enhanced BDS. In this work, the performance improvement mechanism was studied in-depth, providing a new strategy for optimizing linear-like lead-free relaxor ferroelectric energy storage properties.

Synergistic optimization of delayed polarization saturation and enhanced breakdown strength in lead-free capacitors for superior energy storage characteristics

High-performance dielectric energy-storage ceramics are indispensable core components in pulsed power systems. Despite progress in enhancing energy storage performance, there are still significant constraints among various macroscopic performance parameters, hindering their miniaturization and integration into devices. Herein, we propose a novel weakly coupled relaxor ferroelectric ceramic system that delays premature polarization saturation of BaTiO3-based ceramics to achieve the desirable energy storage characteristics. The ceramic exhibits a high energy storage density (Wrec) of ∼4.58 J cm−3 and high energy efficiency (η) of ∼95.2 % under an electric field of 540 kV cm−1, along with good performance stability in the range of 40–160 °C and 1–120 Hz. Furthermore, the enhanced insulation properties and refined average grain size contribute to the high breakdown field strength (Eb) of the system. These findings provide a viable framework for the design of dielectric ceramic capacitors with high energy-storage characteristics.

Superior energy storage properties of BiFeO3 doped NaNbO3 antiferroelectric ceramics

NaNbO3 (NN)-based dielectric ceramics for energy storage have garnered significant interest due to their high saturation polarization, low residual polarization, and superior breakdown strength (Eb). However, the low recoverable energy storage density (Wrec) and efficiency (η) significantly limited their practical application. Herein, BiFeO3 (BF) was incorporated into NN to optimize the energy storage performance. The NN-BF ceramics exhibited pronounced antiferroelectric (AFE) relaxor phase, alongside grain size reduction and Eb enhancement, which contributed to a significant increase of Wrec and η. Specially, the optimum Wrec of 4.43 J/cm³ and η of 71.51 % were achieved at the composition of 0.9NN-0.1BF. Besides, stable energy storage performance was maintained over a wide temperature range (20–120 °C). These results highlight the potential of NN-BF relaxor AFE ceramics as promising candidates for high-performance energy storage applications.

Energy storage properties, transmittance and hardness of Er doped K0.5Na0.5NbO3-based ceramics

Transparent energy storage ceramics can balance energy storage characteristic and optical characteristic, and are expected to be used in areas such as transparent pulse capacitors. However, excellent energy storage performance and dramatic light transmittance are difficult to achieve simultaneously, limiting their subsequent development in the actual applications. The paper proposes a way to improve the transparent energy storage properties of KNN-based samples by regulating domain and grain size. By introducing an appropriate amount of Er2O3, fine cube grains and nanodomains are constructed. When doping 0.20 mol% Er2O3, the ceramics exhibited excellent recoverable energy storage density Wrec ∼ 6.2 J/cm3, superior energy-storage efficiency η ∼ 71.3 %, large dielectric breakdown strength Eb ∼ 670 kV/cm, ultrahigh hardness value of 6.9 GPa, and a maximum transmittance T ∼72 % at 880 nm. Dense microstructure, nanoscale grains, symmetrical lattice structure and relaxor behavior are the main reasons for obtaining high energy storage and transparency properties.

PYN-based antiferroelectric ceramics with superior energy storage performance within an ultra-wide temperature range

Antiferroelectric (AFE) ceramics are known for their rich field-induced phase transitions, which mainly contribute to their superior energy storage performance. However, the phase transitions instability caused by high temperature often limits its application scenarios. Developing AFE ceramics with high energy storage properties and wide application temperature ranges is challenging. Here, considering the B-site ordering characteristics of Pb(Yb0.5Nb0.5)O3, we propose a simple approach for introducing A-site distortion and adjusting B-site ordering to confront these challenges. In our Fe3+/Sr2+co-doping system, we realized an ultra-wide temperature range of 25–200 °C, within which the recoverable storage density was considerable: 8.48–13.39 J cm−3. In this interval, the discharge energy density could reach 6.15–9.67J cm−3, and the discharge current density and discharge power density were 755.09–1667.36 A cm−2 and 207.65–500.21 MW cm−3, respectively. The obtained high-temperature energy storage performance was superior to that of existing energy storage ceramics or polymer films. The introduction of A-site distortion improves the stability of AFE phase, the decrease in B-site ordering suppresses the remanent polarization and delays change in structural symmetry with temperature. This study forms a basis for further applications of dielectric capacitors and signifies the development of wide-temperature-range energy storage devices.

Improvement of energy storage properties of NN-based ceramics by high-entropy strategy and A-site cation vacancies

High-entropy dielectric capacitors have recently drawn increasing attention in the field of energy storage. In this study, NiO has been incorporated into [(Na0.7Bi0.1)0.8Sm0.02Ca0.02Sr0.02Ba0.02]Nb0.8Sb0.1Ta0.1O3-based ceramics. We applied the concept of high-entropy design to introduce cation vacancies at the A-site, enhancing conformational entropy. This approach led to the successful preparation of a novel type of energy-storage ceramics with an ABO3 perovskite structure, denoted as (1-x)NBSCSBNST-xNiO (x = 0, 0.02, 0.04, & 0.06). We conducted a systematic study of the microstructural, dielectric, and ferroelectric characteristics, along with an exploration of the influence of the high-entropy strategy on their performance. The ΔSconfig increases with NiO doping, and the Eb of the NBSCSBNST-0.02Ni sample exhibits a significant increase to 730 kV/cm from 550 kV/cm of NBSCSBNSTN. This enhancement is accompanied by a recoverable energy density (Wrec) of 4.43 J/cm3 and an efficiency (η) of 75.9 %. As the content of NiO increases from x = 0 to x = 0.06, the phase transition diffusion behavior strengthens. Additionally, the permittivity (εr) spectrum becomes more uniform, and the activation energy of the prepared ceramic samples increases from 1.03 eV to 1.76 eV. This effect suppresses the emergence of localized electric branching, eventually improving the breakdown strength of NBSCSBNST-xNi ceramic materials. The obtained results indicate that the concept of high-entropy design to introduce cation vacancies at the A-site is an efficient approach to improve the energy storage characteristics of lead-free dielectric capacitors.

Effect of different rare-earth dopings of KNN-based transparent energy storage ceramics

Rare-earth elements [Formula: see text]-, [Formula: see text]-, [Formula: see text]- and [Formula: see text]-doped ([Formula: see text][Formula: see text])[Formula: see text][Formula: see text][Formula: see text][Formula: see text]O3 ceramics (abbreviated as KNLNB-0.1%RE) were prepared by conventional solid-phase sintering method. The structure, transparency, energy storage and photoluminescence properties of the samples are investigated. All ceramics have the pseudo-cubic phase structure without the impurity phase at room temperature. KNLNB-0.1%RE ceramics exhibit excellent optical transmittance, with KNLNB-0.1%Ho achieving 71.8% transmittance in the visible wavelength range (780[Formula: see text]nm) and largest effective energy storage density of 1.45[Formula: see text]J/cm3. In our experiments, rare-earth-doped KNLNB ceramics exhibit photoluminescence effects. This work facilitates the development of transparent energy storage ceramics with fluorescent effects.

Mechanism and simulation analysis of high electric field of NaNbO3 − based energy storage ceramics based on defect engineering design

Ceramic materials possessing high polarization and substantial breakdown electric fields represent a principal strategy for enhancing the performance of pulse power systems. To augment the energy storage capabilities of ceramic materials, numerous studies have suggested a variety of specific control methods. However, reports on the vacancy defects arising during the regulatory process and the relationship between these vacancy defects and energy storage performance are scarce. This paper introduces an optimal quantity of oxygen vacancy defects into the prepared NN–based ceramics for characterization and analysis, aiming to elucidate the impact of oxygen vacancy defects and their concentration on the structure and energy storage properties of ceramics. Through managing the content of oxygen vacancies, the 0.83NN–0.17SNS ceramic achieved a high energy storage density (Wrec) of 6.27 J/cm3 and an energy storage efficiency (η) of 82.79 % at 705 kV/cm. This work presents a novel approach to regulating the energy storage performance, offering a new method for optimizing the performance of lead-free energy storage materials.

Realizing Outstanding Energy Storage Performance in KBT-Based Lead-Free Ceramics via Suppressing Space Charge Accumulation.

The great potential of K1/2Bi1/2TiO3 (KBT) for dielectric energy storage ceramics is impeded by its low dielectric breakdown strength, thereby limiting its utilization of high polarization. This study develops a novel composition, 0.83KBT-0.095Na1/2Bi1/2ZrO3-0.075 Bi0.85Nd0.15FeO3 (KNBNTF) ceramics, demonstrating outstanding energy storage performance under high electric fields up to 425kVcm-1: a remarkable recoverable energy density of 7.03Jcm-3, and a high efficiency of 86.0%. The analysis reveals that the superior dielectric breakdown resistance arises from effective mitigation of space charge accumulation at the interface, influenced by differential dielectric and conductance behaviors between grains and grain boundaries. Electric impedance spectra confirm the significant suppression of space charge accumulation in KNBNTF, attributable to the co-introduction of Na1/2Bi1/2ZrO3 and Bi0.85Nd0.15FeO3. Phase-field simulations reveal the emergence of a trans-granular breakdown mode in KNBNTF resulting from the mitigated interfacial polarization, impeding breakdown propagation and increasing dielectric breakdown resistance. Furthermore, KNBNTF exhibits a complex local polarization and enhances the relaxor features, facilitating high field-induced polarization and establishing favorable conditions for exceptional energy storage performance. Therefore, the proposed strategy is a promising design pathway for tailoring dielectric ceramics in energy storage applications.

Antiferroelectricity of titanite-type oxide SrTiGeO5 and its potential for power electronics applications

Antiferroelectric materials have recently received renewed attention due to the increased demand for energy-storage ceramics and power electronics applications. This study demonstrates antiferroelectricity in a titanite-type oxide, SrTiGeO5, through direct observation of a double D-E hysteresis loop by polarization measurements. Temperature dependence of dielectric permittivity shows a cusp around 550 K, indicating a relatively high antiferroelectric phase transition temperature for SrTiGeO5. It is suggested that an electric-field-induced rise of permittivity in SrTiGeO5 has the potential for application in protective circuits of power electronics devices. The present study paves the way for the development of innovative antiferroelectric applications.

Ultrafast discharge properties and enhanced energy density in lead‐free NaNbO3‐based relaxor ferroelectric ceramics

AbstractNaNbO3‐based (NN) energy storage ceramics are known for exhibiting high maximum polarization (Pmax) and large recoverable energy density (Wrec). However, the huge energy loss density (Wloss) has been a limiting factor in improving energy storage performance. Therefore, a ternary system was designed to achieve both huge Wrec and efficiency (η). The combination of 0.35Bi(Zn0.5Ti0.5)O3–0.65BaTiO3 (BZTBT) was chosen to reduce grain size and disrupt the long‐range ordered domains, thereby inducing the polar‐nano‐regions to mitigate Wloss. The optimal performance was achieved with the 0.75NaNbO3–0.25(0.35Bi(Zn0.5Ti0.5)O3–0.65BaTiO3) (0.75NN–0.25BZTBT) ceramic, which exhibited a high Wrec = 2.68 J/cm3 and superior η = 82.7% under 310 kV/cm. Remarkably, the 0.75NN–0.25BZTBT ceramic displayed an exceptionally fast discharge time to 90%, t0.9 = 88 ns, coupled with a huge energy density Wd = 0.95 J/cm3. This study demonstrates the significant potential of 0.75NN–0.25BZTBT ceramic in the realm of energy storage and rapid charge–discharge applications.

Achieving High Energy Storage Performance under a Low Electric Field in KNbO3-Doped BNT-Based Ceramics.

Ceramic capacitors have great potential for application in power systems due to their fantastic energy storage performance (ESP) and wide operating temperature range. In this study, the (1 - x)Bi0.5Na0.47Li0.03Sn0.01Ti0.99O3-xKNbO3 (BNLST-xKN) energy storage ceramics were synthesized through the solid-phase reaction method. The addition of KN disrupts the long-range ferroelectric order of the BNLST ceramic, inducing the emergence of polar nanoregions (PNRs), which enhances the ESP of the ceramics. The BNLST-0.2KN ceramic demonstrates a high recovered energy density (Wrec ∼ 3.66 J/cm3) and efficiency (η ∼ 85.8%) under a low electric field of 210 kV/cm. Meantime, it exhibits a large current density (CD ∼ 831.74 A/cm2), high power density (PD ∼ 78.86 MW/cm3), and fast discharge rate (t0.9 ∼ 0.1 μs), along with good temperature stability and excellent fatigue stability. These properties make the BNLST-0.2KN ceramic a promising candidate for energy storage applications in low electric fields.

Structural phase coexistence enhances the energy storage density of (Bi0.5Na0.5)0.8Ba0.2Ti1-ySnyO3 lead-free ceramics

In the present study, BaSnO3 was introduced into polycrystalline NBT-BT ferroelectric ceramics and conducted a comprehensive investigation into the structural, dielectric, ferroelectric, and energy storage characteristics of the (Bi0.5Na0.5)0.8Ba0.2Ti1-ySnyO3 (BNBTS) ceramics. The coexistence of structural phases P4mm and Amm2 was observed through Rietveld refinement and also confirmed by Raman analysis. The formation energy decreases with an increase in substitution concentration favouring the formation of the orthorhombic phase. The SEM analysis revealed a denser microstructure characterised by smaller grain sizes, which favourably enhances energy storage density. Furthermore, Raman spectroscopic analysis unveiled a softening of Ti–O bonds, indicating the emergence of macroscopic relaxor behaviour. Dielectric studies provided evidence of a transition from ferroelectric to relaxor behaviour, an observation further confirmed by P-E loop measurements. This transition can be linked to the partial substitution of Sn4+ ions for Ti4+ ions, disrupting the ferroelectric long-range order within the matrix phase. Notably, the polarization-electric field (P-E) loop of BNBTS2 ceramics exhibited a substantial value of polarization (Ps) 30 μC/cm2 with a reduced value of remnant polarization (Pr) 2.29 μC/cm2. These characteristics contributed to the achievement of higher energy recovery (Wrec) and lower energy loss (Wloss) values, measuring 1.184 J/cm3 and 0.142 J/cm3, respectively, with a notable efficiency of 88.8%. Consequently, the system of ternary ceramics demonstrates promise as a potential option for energy storage ceramics among NBT-BT-based materials.

Bi0.5Na0.5TiO3-based energy storage ceramics with excellent comprehensive performance by constructing dynamic nanoscale domains and high intrinsic breakdown strength

Lead-free ceramic-based dielectric capacitors show huge potential in electrical energy storage in pulsed power systems due to their fast charge/discharge rate, ultrahigh power density and environmental friendliness. However, unsatisfied charge/discharge performance characterized by inferior recoverable energy storage density (Wrec generally <5 J/cm3) has become a key bottleneck to restrict their applications in cutting-edge energy storage devices. In this paper, we focus on simultaneously realizing ultrahigh Wrec and efficiency (ƞ) in eco-friendly Bi0.5Na0.5TiO3 (BNT)-based dielectric ceramics via chemical doping. Interestingly, highly dynamic polar nanoregions (PNRs) and nanodomains are constructed by incorporating Sr0.7Nd0.2TiO3 (SNT) into 0.94BNT-0.06BaTiO3. Of great importance, the resulting relaxor ferroelectrics (RFEs) exhibit high bulk resistivity, submicron grain size and wide band gap due to high level of SNT doping accompanying with 1 at% Nb donor doping. Therefore, excellent energy storage properties with ultrahigh Wrec∼8.08 J/cm3 and ƞ∼92.1% are achieved due to coexistence of large polarization difference (ΔP=Pmax−Pr) and giant dielectric breakdown electric field (Eb∼540 kV/cm). Furthermore, excellent temperature/frequency/cycling stability characterized by ΔWrec < ±4% and Δη < ±2% ensure the energy storage applications of the studied dielectric ceramics over an enormous range of scales.

Nanoscale structural heterogeneity enhanced temperature-stable energy storage in Bi0.5Na0.5TiO3-based relaxor ceramics via domain and defect dipoles engineering

Ceramic-based dielectric capacitors are showing great potential in advanced high-power applications. However, simultaneous achievement of high energy density (Wrec) and temperature stability is still a main bottleneck. Herein, an extraordinary nanoscale structural heterogeneity is developed to promote temperature-stable energy storage in Er/Mn co-doped Bi0.5Na0.5TiO3 based ceramics via domain and defect dipoles engineering. The composition-driven domain reconstruction by Er/Mn co-doping can induce internal random fields with rapid response to the electric field, and thus enhance ΔP and η. Meanwhile, the donor-accpetor Er/Mn doping could manipulate defect dipoles coupling to resist the applied field evolution to elevate BDS and η. Besides, the improved relaxor feature and core-shell structure give rise to the enhanced temperature stability. Ceramics with 2 mol % Er2O3 demonstrate high Wrec ∼2.79 J/cm3, large efficiency ∼89.4% and outstanding dielectric stability within 70–500 °C. The proposed nanostructural heterogeneity was verified as a promising pathway to manufact temperature-stable energy storage ceramics.

Samarium-modified PLZST-based antiferroelectric energy storage ceramics for low-temperature sintering in reducing atmosphere

The energy storage properties of pure PLZST-based antiferroelectric ceramics are excellent; however, the high sintering temperature renders them unsuitable for co-firing with copper inner electrodes as MLCC dielectric materials. The proven BASK glass additive was employed in this study to lower the sintering temperature of PLSZT ceramics, while simultaneously doping Sm3+ ions to enhance their sintering performance under reducing atmospheres. The precise evaluation process confirmed that the addition of glass effectively reduced the sintering temperature to 1040 °C. Furthermore, the defect association of Sm3+ doping hindered the formation of oxygen vacancies, facilitated ceramic grain growth, and significantly enhanced insulation resistivity. Consequently, an ultrahigh recoverable energy density (Wrec) of 5.19 J/cm3 with a high energy storage efficiency (η) of 94.5% are achieved at an electric field of 430 kV/cm. Moreover, the AFE ceramics possess excellent discharge energy storage properties with a high discharge energy density (Wd) of 4.26 J/cm3 and a large power density (Pd) of 139 MW/cm3.

Intrinsic and extrinsic contributions to energy storage performance in potassium sodium niobate–based ceramics

AbstractBoth the intrinsic and extrinsic contributions to the high energy storage properties of (K0.5Na0.5)NbO3 were investigated herein by employing Bi(Mg2/3Ta1/3)O3 as a second component to synthesize novel environment‐friendly energy storage ceramics. The role of the second component was confirmed to reduce the intrinsic activation of electrons, which effectively improves the band gap values and reduces the probability of intrinsic breakdown. Phase field simulation was employed to confirm that the smaller grain size of the modified ceramic microstructure enhances the extrinsic breakdown and dielectric breakdown strength. Moreover, ab initio molecular dynamics were used to investigate the critical role of the Mg ions in lowering the initial polarization and forming nanodomains, representing the intrinsic contribution to decreasing the initial polarization. An intrinsic structure with moderate polarization rapidly increases the polarization of ceramics under external electric fields, facilitating high energy storage density. The prepared ceramics achieve a recoverable energy density (Wrec) of 3.86 J/cm3 and energy efficiency (η) of 81.2% at 385 kV/cm.