Enhanced energy storage performances of Bi(Ni1/2Sb2/3)O3 added NaNbO3 relaxor ferroelectric ceramics

In the development of dielectric ceramic materials, the requirements of miniaturization and integration are becoming increasingly prominent. How to obtain greater capacitance in a smaller volume is one of the important pursuits. In this paper, lead-free (1-x)NaNbO₃-xBi(Ni_1/2Sb_2/3)O₃(xBNS) with high recoverable energy storage density (W_rec) and relatively high energy storage efficiency(η) were prepared by a solid state sintering method. Bi(Ni_1/2Sb_2/3)O₃ was introduced into the Sodium niobate ceramics(NN)-based ceramics to reduce the sintering temperature and increase the maximum breakdown field strength (E_b). Finally, 0.15BNS achieved a high E_b of 460 kV/cm, W_rec of 3.7 J/cm³ and η of 77%. In addition, the sample maintained excellent stability in the frequency range of 1–120 Hz. And the 0.15BNS ceramics also exhibited high power density (P_D = 36.4 MW/cm³), large current density (C_D = 520.8 A/cm²) and relatively fast charge-discharge rate (t_0.9 = 1050 ns). These results demonstrate the potential application value of xBNS ceramics in energy storage capacitors.     

Large energy density with excellent stability in fine-grained (Bi0.5Na0.5)TiO3-based lead-free ceramics

In this work, fine-grained (0.95-x)(Bi_0.5Na_0.5)TiO₃-0.05BaTiO₃-xBi(Zn_2/3Nb_1/3)O₃ (abbreviated as BNT-BT-xBZN, x = 0～0.20) lead-free ceramics are successfully prepared, showing a high energy storage performance. The addition of BZN results in decreased grain size, enhanced breakdown strength and stronger relaxor behavior with polar nanoregions. Slimmer P-E loops are thereby achieved, leading to the improvement of energy density and efficiency. As a result, a high W_D of ～2.83 J/cm³ is achieved under a relatively low electric field of 18 kV/mm in the x = 0.125 ceramic with submicron-sized grains (～0.4 μm). The W_D value is larger than that of x = 0 ceramic by ～800%. Furthermore, the x = 0.125 ceramic possesses excellent frequency stability and strong fatigue endurance. The BNT-BT-xBZN lead-free ceramics show promising potential for application in high energy density ceramic capacitors.     

Piezoelectric properties of (1-x)BZT-xBCT system for energy harvesting applications

In this study, we investigated (1-x)Ba(Zr_0.2Ti_0.8)O₃–x(Ba_0.7Ca_0.3)TiO₃ lead-free piezoelectric ceramics for energy harvester applications. The (1-x)BZT-xBCT ceramic is a promising lead-free piezoelectric material in the field of piezoelectric energy harvesting. Piezoelectric and energy properties of (1-x)BZT-xBCT ceramics were analyzed to confirm the possibility of using them as energy-harvesting materials. Especially, the vicinity of the phase convergence region was investigated to improve their piezoelectric properties. In the phase convergence region, cubic, rhombohedral, orthorhombic, and tetragonal regions co-exist within the narrow region. Near the phase transition region between the orthorhombic and tetragonal phase, the highest piezoelectric property d₃₃?=?464 pC/N and the highest energy density of 158.5 μJ/cm³ were observed. This output energy density of 158.5 μJ/cm³ is the recorded highest value among lead-free ceramics. We found that the optimal sintering temperature was 1475?°C and the optimal composition was BZT-0.5BCT.     

Na0.5Bi0.5TiO3-based ferroelectric relaxor with high thermal stability and anti-fatigue for charge-discharge properties

Apart from discharge energy density (W_r) and discharging time (t_0.9), thermal stability and anti-fatigue for charge-discharge performance are also the important performance indexes for dielectric pulsed capacitor. Na_0.5Bi_0.5TiO₃ based ceramics are usually accompanied by huge electric field-induced strain when appling electric field, resulting in the fatigue phenomenon and thermal accumulation effect in the cycling process. In this work, Na_0.5Bi_0.5TiO₃-xNaNbO₃ (NBT-xNN) ferroelectric relaxor ceramic has been prepared by the solid state reaction process. The effect of NaNbO₃ content on microstructures, impedance spectroscopy, electric-field-induced strain and charge-discharge performance of NBT-xNN ceramics have been investigated systematically. Results indicate the proper percent of NaNbO₃ could favor the formation of polar nanoregions (PNRs), which leads to the diffusion of phase transition and the diminution of electromechanical strain. Therefore, the high thermal stability and anti-fatigue for charge-discharge property has been achieved in NBT-xNN ceramics. An enhanced discharging energy density of 2.44 J cm^?3 along with discharge time of 0.31 μs could be obtained in the NBT-xNN with x = 0.3, and a very stable discharge energy density of 2.06 J cm^?3 concomitantly with discharge time less than 0.37 μs could be gained in a wide temperature range of 20–150 °C with a fluctuation of ±4% after 10⁴ charge/discharge cycles. This work would contribute to the development of charge-discharge system, especially dielectric capacitor, for green pulsed power devices.     

An alternative way to design excellent energy-storage properties in Na0.5Bi0.5TiO3-based lead-free system by constructing relaxor dielectric composites

With growing concerns over environmental protection, lead-free dielectric ceramic capacitors are attracting much attention. In this work, a series of novel (1-x) Na_0.5Bi_0.5TiO₃-x Ba₅LaTi₃Ta₇O₃₀ ((1-x)NBT-xBLTT) dielectric composite ceramics were fabricated by a traditional solid‐state method. All the samples possess a compact microstructure with refined grain morphology with increasing BLTT content, and tend to exhibit a diphase dielectric composite as x reaches up to 0.05. Furthermore, the addition of BLTT enhances the dielectric relaxor behavior of NBT-based ceramics, such that the x = 0.15 composite ceramic exhibits a typical feature of relaxor ferroelectrics. As a result, a high recoverable energy-storage density of W_rec~3.67 J/cm³, an ultrahigh energy-storage efficiency of η~97.3%, and a high power density of P_D~333 MW/cm³ can be simultaneously obtained in the x = 0.15 relaxor composite ceramic. This study provides an alternative way to design excellent energy-storage performances in NBT-based compositions through constructing dielectric relaxor composites via introducing non-polar tungsten bronze oxides.     

Simultaneously enhanced energy storage density and efficiency in novel BiFeO3-based lead-free ceramic capacitors

In this work, a series of novel lead-free (1-x)Bi_0.83Sm_0.17Fe_0.95Sc_0.05O₃-x(0.85BaTiO₃-0.15Bi(Mg_0.5Zr_0.5)O₃) [(1-x)BSFS-x(BT-BMZ), x = 0.45?0.85] relaxor ceramics were prepared by solid phase sintering, and their dielectric properties and energy storage performances were explored. It was revealed that all the samples have a dense structure with pure pseudo-cubic phase. With the increase of x, the ferroelectric hysteresis loop is gradually slimmed accompanied by a decreasing polarization, indicating an enhanced relaxor behavior. Moreover, the electric breakdown strength increases linearly with x due to the fine grain size and enhanced relative density. Interestingly, a large recoverable energy density (～3.2 J/cm³) with an outstanding efficiency (～92 %) is achieved under an electric field ～206 kV/cm for the optimized component x = 0.75, which is superior to other reported lead-free ceramic systems. Moreover, the optimized ceramics of 0.25BSFS-0.75(BT-BMZ) show good thermal stability (25?100 °C) and excellent fatigue endurance (cycle number: > 10⁵) in energy storage performances. This work opens up a new route to tailor lead-free dielectric ceramics with high energy storage properties.     

High energy storage and ultrafast discharge in NaNbO3-based lead-free dielectric capacitors via a relaxor strategy

Dielectric capacitors with decent energy storage and fast charge-discharge performances are essential in advanced pulsed power systems. In this study, novel ceramics (1-x)NaNbO₃-xBi(Ni_2/3Nb_1/3)O₃(xBNN, x = 0.05, 0.1, 0.15 and 0.20) with high energy storage capability, large power density and ultrafast discharge speed were designed and prepared. The impedance analysis proves that the introducing an appropriate amount of Bi(Ni_0·5Nb_0.5)O₃ boosts the insulation ability, thus obtaining a high breakdown strength (E_b) of 440 kV/cm in xBNN ceramics. A high energy storage density (W_total) of 4.09 J/cm³, recoverable energy storage density (W_rec) of 3.31 J/cm³, and efficiency (η) of 80.9% were attained in the 0.15BNN ceramics. Furthermore, frequency and temperature stability (fluctuations of W_rec ≤ 0.4% over 5–100 Hz and W_rec ≤ 12.3% over 20–120 °C) were also observed. The 0.15BNN ceramics exhibited a large power density (19 MW/cm³) and ultrafast discharge time (~37 ns) over the range of ambient temperature to 120 °C. These enhanced performances may be attributed to the improved breakdown strength and relaxor behavior through the incorporation of BNN. In conclusion, these findings indicate that 0.15BNN ceramics may serve as promising materials for pulsed power systems.     

A-site compositional modulation in barium titanate based relaxor ceramics to achieve simultaneously high energy density and efficiency

Dielectric ceramics capacitors (DCC) with excellent energy storage performance (ESP) and charge-discharge performance (CDP) is very critical in the field of advanced electronics and power systems. A strategy that improves the ESP of 0.6Ba(Zr_0.2Ti_0.8)O₃-0.4(Na_0.5Bi_0.5)TiO₃ (BZT-NBT) ceramics was proposed via Sr²⁺ doping. XRD and SEM results confirmed that 0.6(Ba_1-xSr_x)(Zr_0.2Ti_0.8)O₃-0.4(Na_0.5Bi_0.5)TiO₃ (x = 0, 0.1, 0.2, 0.3, 0.4) (BSZT-NBT) ceramics formed dense and stable perovskite solid solutions. The relaxor ferroelectric (RFE) properties of BSZT-NBT ceramics were also well proved by dielectric behaviors. A large recoverable energy storage density (W_rec) and large efficiency (η) of 3.72 J cm⁻³ and 94.03 % (x = 0.3) can be simultaneously obtained at 289 kV cm^-1. ESP of BSZT-NBT (x = 0.3) ceramics at 180 kV cm^-1 exhibit good frequency (1−100 Hz) and temperature (room temperature (RT)-120 °C) stability. BSZT-NBT (x = 0.3) ceramics at 120 kV cm⁻¹ exhibit a prominent power density (P_D) and rapid discharge rate (t_0.9) of of 37.62 MW cm⁻³ and 70.6 ns. All evidences confirm that introduction of Sr²⁺ into A-site of barium titanate-based ceramics could effectively improve ESP.     

Decreasing polar-structure size: Achieving superior energy storage properties and temperature stability in Na0.5Bi0.5TiO3-based ceramics for low electric field and high-temperature applications

It is a grand challenge to achieve high energy density (W) and efficiency (η) simultaneously under a low electric field (LE) to obtain new high energy storage capacitors. Similar to anti-ferroelectrics, the (1-x)NBT-xBaMg_1/3Nb_2/3O₃ relaxor material exhibits a non-linear dependence on electric field, which is caused by a reversible field-induced phase transition. This leads to high W (2.37 J/cm³) and η (81.5 %) under a LE of 155 kV/cm, which makes it superior to other bulk ceramics. Combining large polarizability of Ba²⁺ in A-site and local structural heterogeneity on the B-site by Mg_1/3Nb_2/3⁴⁺, enhanced relaxor behavior and decreased polar-structure size were induced in (1-x)NBT-xBaMg_1/3Nb_2/3O₃ ceramics. The permittivity, nevertheless, stays high at ～2273±15 %. Furthermore, the electrical properties become stable in a wide temperature range from 44?396 °C for the sample with x=0.15. In addition, high current density/C_D (450 A/cm²), power density/P_D (23 MW/cm³) and discharge density/W_D (0.57 J/cm³) were realized tested with pulse discharge testing. Our work will provide a development guidance for dielectric energy storage ceramics at low field and high fields with excellent temperature stability.     

Ultrahigh storage density achieved with (1-x)KNN-xBZN ceramics

A series of (1-x)K_0.5Na_0.5NbO₃-xBa(Zn_1/3Nb_2/3)O₃ ((1-x)KNN-xBZN) nanostructural ceramics was successfully synthesised via solid-state reactions. These nanostructural ceramics exhibited high energy storage density compared with pure KNN ceramics. Further analysis of their dielectric/ferroelectric properties and structures revealed that the addition of BZN alloy disrupted the long-range order of the ferroelectric lattice of pure KNN and favoured the formation of ferroelectric islands and/or polar nano-regions. Consequently, the nanostructured ceramic with x = 0.05 exhibited ultrahigh energy storage density, W, of approximately 9.14 J/cm³ and recoverable energy storage density, W_rec, of approximately 4.87 J/cm³ under a fairly low applied electrical field (220 kV/cm). These values exceed the highest values ever reported for KNN-based bulk ceramics. In addition, both excellent fatigue endurance (10⁵ cycles) and temperature stability (Δε'/ε_100°C < 15 % in the range 30–390 °C) were realised with the 0.97KNN-0.03BZN ceramic. Their excellent energy storage properties render KNN-based ceramics potential candidates for application in pulsed-power systems.     

High energy storage properties of lead-free Mn-doped (1-x)AgNbO3-xBi0.5Na0.5TiO3 antiferroelectric ceramics

In this work, 0.2 wt.% Mn-doped (1-x)AgNbO₃-xBi_0.5Na_0.5TiO₃ (x = 0.00–0.04) ceramics were synthesized via solid state reaction method in flowing oxygen. The evolution of microstructure, phase transition and energy storage properties were investigated to evaluate the potential as high energy storage capacitors. Relaxor ferroelectric Bi_0.5Na_0.5TiO₃ was introduced to stabilize the antiferroelectric state through modulating the M₁-M₂ phase transition. Enhanced energy storage performance was achieved for the 3 mol% Bi_0.5Na_0.5TiO₃ doped AgNbO₃ ceramic with high recoverable energy density of 3.4 J/cm³ and energy efficiency of 62% under an applied field of 220 kV/cm. The improved energy storage performance can be attributed to the stabilized antiferroelectricity and decreased electrical hysteresis ΔE. In addition, the ceramics also displayed excellent thermal stability with low energy density variation (<6%) over a wide temperature range of 20−80 °C. These results indicate that Mn-doped (1-x)AgNbO₃-xBi_0.5Na_0.5TiO₃ ceramics are highly efficient lead-free antiferroelectric materials for potential application in high energy storage capacitors.     

Improved dielectric energy storage performance of Na0.5Bi0.5TiO3–Sr0.7Nd0.2TiO3 lead-free ceramics by adding an appropriate amount of AgNbO3

Based on the significant advantages of dielectric ceramics in high power energy storage, (1-x) (0.55Bi_0.5Na_0.5TiO₃-0.45Sr_0.7Nd_0.2TiO₃)-xAgNbO₃ (NBSNT-xAN) ceramics were prepared by traditional solid phase method. The introduction of AN in NBSNT ceramics not only increased the degree of relaxation, but also refined the grain size, enhanced the BDS, and finally improved the energy storage performance. It is found that the NBSNT-0.5AN ceramics obtained an effective energy storage density as high as 3.08 J/cm³ and an efficiency of 79.94%. In addition, good thermal stability and temperature stability were exhibited in the range of 30–120 °C and 10–350 Hz, and at the same time, it performed very well in the pulsed test at room temperature and variable temperatures. This provides a design idea for the miniaturization and integration of energy storage ceramic materials.     

Excellent thermal stability,high efficiency and high power density of (Sr0.7Ba0.3)5LaNb7Ti3O30–based tungsten bronze ceramics

A series of (1-x)(Sr_0.7Ba_0.3)₅LaNb₇Ti₃O₃₀–x(Bi_0.5Na_0.5)TiO₃ (x = 0.1–0.4) ceramics with tungsten bronze structure were prepared by solid state reaction. Phase composition, microstructure and energy storage properties were studied. When x = 0.3, excellent thermal stability satisfying the X7R specification was obtained and its energy storage as well as charge-discharge performances were further evaluated. Release energy density (W_re) of 0.77 J/cm³ and an energy storage efficiency of 97.3 % were detected at a low electric field of 20 kV/mm. Under the electric field of 10 kV/mm, the change of W_re in the temperature range of −55 °C to 125 °C is less than 15 % compared to room temperature. Short discharge period (∼0.17 μs), high power density (61.2 MW/cm³) and high discharge energy density (2.45 J/cm³) were evaluated by charge-discharge tests. Excellent thermal stability, high energy storage efficiency and high power density indicate that 0.7(Sr_0.7Ba_0.3)₅LaNb₇Ti₃O₃₀–0.3(Bi_0.5Na_0.5)TiO₃ ceramic is a promising pulse capacitor for working over a wide temperature range.     

Enhanced energy storage properties of Bi(Ni2/3Nb1/6Ta1/6)O3–NaNbO3 solid solution lead-free ceramics

Sodium niobate energy storage ceramics with good environmental performance are widely used in electric power conversion and pulse power system, large energy storage density and high efficiency, huge power density and charge and discharge faster. In this work, (1-x)NaNbO₃-xBi(Ni_2/3Nb_1/6Ta_1/6)O₃ [(1-x)NN-xBNNT] (0.12 ≤ x ≤ 0.18) ceramics system were prepared by solid state reaction method. By introducing Bi(Ni_2/3Nb_1/6Ta_1/6)O₃ (BNNT), a relaxation strategy was constructed, which significantly improved the energy storage properties of NaNbO₃ (NN) based ceramics. Finally, comparatively high recoverable energy density (W_rec) of 3.43 J/cm³ and large energy storage efficiency (η) of 83.3% were obtained in 0.86NN-0.14BNNT ceramics. Besides discharge energy density (W_d) of 0.69 J/cm³, ultra fast charge-discharge rate (t_0.9) of 55 ns, the power density (P_D) of 70.66 MW/cm³ and the current density (C_D) of 883.23 A/cm² were also observed in ceramic.     

Energy storage properties in Bi(Mg1/2Sb2/3)O3-doped NaNbO3 lead-free ceramics

Sodium niobate energy storage ceramics with high energy density and efficiency can be used as potential candidate materials for pulse power devices. Doping modification of dielectric ceramic matrixes is an effective means to obtain high performance. The (1-x)NaNbO₃-xBi(Mg_1/2Sb_2/3)O₃ ceramics were designed in this work. And 0.85NaNbO₃-0.15Bi(Mg_1/2Sb_2/3)O₃ showed a large W_rec of 4.65 J/cm³ at an E_b of 580 kV/cm. Excellent frequency stability of W_rec (1.67–1.7 J/cm³) and η (86%–89.1%) over frequency range of 1–100Hz was observed. Further, good temperature stability of W_rec (1.5–1.71 J/cm³) and η (68%–87%) over abroad temperature range of 20–180 °C was attained successfully. In addition, excellent power density (P_D = 113 MW/cm³), large current density (C_D = 1255 A/cm²) and discharge speed (0.51μs) were obtained, which demonstrates the great potential practical value of this ceramic in the energy storage applications.     

Achieving excellent energy storage density of Pb0.97La0.02(ZrxSn0.05Ti0.95-x)O3 ceramics by the B-site modification

The applications of antiferroelectric (AFE) materials in miniaturized and integrated electronic devices are limited by their low energy density. To address the above issue, the antiferroelectricity of the reinforced material was designed to improve its AFE-ferroelectric (FE) phase transition under electric fields. In this present study, the composition of Zr⁴⁺ (0.72 Å) and Ti⁴⁺ (0.605 Å) at B-site of Pb_0.97La_0.02(Zr_xSn_0.05Ti_0.95-x)O₃ ceramics with orthogonal reflections are synthesized via the tape-casting method. These ceramics are modified to enhance their antiferroelectricity by reducing their tolerance factor. A recoverable energy storage density W_rec 12.1 J/cm³ was obtained for x = 0.93 under 376 kV/cm, which is superior value than reported until now in lead-based energy storage systems. Moreover, the discharge energy density can reach 10.23 J/cm³, and 90 % of which can be released within 5.66 μs. This work provides a new window and potential materials for further industrialization of pulse power capacitors.     

Structure,dielectric properties of novel Ba(Zr,Ti)O3 based ceramics for energy storage application

(1-x) Ba(Zr_0.2Ti_0.8)O₃-x Na_0.5Bi_0.5TiO₃ (x = 0, 10, 20 30, 40, 50 mol%) (BZTN) ceramics are prepared by the traditional solid phase method. All BZTN ceramics exhibit a pseudo-cubic BZT based perovskite structure. Both the average grain size and the relaxor ferroelectricity of BZTN ceramics gradually increase with increasing NBT content. The W_rec of 3.22 J/cm³ and η of 91.2% is obtained for the BZTN40 ceramic at 241 kV/cm. BZTN40 ceramic also exhibits good temperature stability from room temperature to 150 °C and frequency stability from 1 Hz to 100 Hz. A P_D of 0.621 J/cm³ and a t_0.9 of 82 ns is obtained for the BZTN40 ceramic at 120 kV/cm. BZTN ceramics show application potential in energy storage and pulse power capacitors.     

High energy storage efficiency of NBT-SBT lead-free ferroelectric ceramics

Ceramic-based dielectrics have been widely used in pulsed power capacitors owing to their good mechanical and thermal properties. Bi_0.5Na_0.5TiO₃-based (NBT-based) solid solutions exhibit relatively high polarization, which is considered as a promising dielectric energy storage material. However, the high remnant polarization and low energy efficiency limit their application in dielectric capacitors. Herein, a typical relaxor ferroelectric Sr_0·7Bi_0·2TiO₃ (SBT) was introduced into the NBT system to strengthen the overall relaxor behavior, resulting in reduced remnant polarization. We prepared (1-x)NBT-xSBT (x = 0.35, 0.45, 0.55, and 0.65) ceramics by the conventional solid-phase reaction method and further investigated their microstructures, dielectric and energy storage properties. With the increase of SBT content, the size of the grains and the maximum dielectric constant gradually decreased, simultaneously. Furthermore, the dielectric shoulder corresponding to the maximum dielectric constant shifted to a lower temperature, indicating that the enhancement of polarization dynamics was a consequence of the domain refinement. As a result, the optimum property was identified in the 0.45NBT-0.55SBT sample with a high recoverable energy density of 1.34 J/cm³ and an outstanding energy efficiency of 96% at a low electric field of 100 kV/cm.     

Realizing high comprehensive energy storage performances of BNT-based ceramics for application in pulse power capacitors

Lead-free ceramic capacitors play an important role in electrical energy storage devices because of their ultrafast charge/discharge rates and high power density. However, simultaneously obtaining large energy storage capability, high efficiency and superior temperature stability has been a huge challenge for practical applications of ceramic capacitors. Here, the relaxor ferroelectric (1-x)[0.8Bi_0.5Na_0.5TiO₃-0.2Ba(Zr_0.3Ti_0.7)O₃]-xSr_0.7La_0.2TiO₃ ((1-x)(BNT-BZT)-xSLT) ceramics are prepared through solid-state reaction method to obtain excellent comprehensive energy storage performances. Particularly, high recoverable energy density (W_rec ～ 2.6 J/cm³) as well as superior efficiency (η ～ 92.2 %) can be achieved simultaneously under 210 kV/cm with composition of x = 0.3. Meanwhile, the corresponding ceramic shows excellent temperature (20?140 °C), frequency (1?200 Hz) and cycle stabilities (10⁶ st). Additionally, the 0.7(BNT-BZT)-0.3SLT ceramic also displays high power density (P_D ～ 38.8 MW/cm³) and extremely short discharge time (τ_0.9 ～ 0.11 μs). Therefore, this study provides a useful guideline for designing novel BNT-based ceramics with superior comprehensive energy storage performances.