Combining high energy efficiency and fast charge-discharge capability in calcium strontium titanate-based linear dielectric ceramic for energy-storage

The high energy density and power density dielectric ceramics with wide frequency and temperature stability are competitive materials for pulse power capacitors. This research proposes an effective strategy for enhancing energy storage performance of Ca_0.5Sr_0.5TiO₃ ceramics through the introduction of Sn⁴⁺ ion. This ion restrains grain growth, increases high insulating grain boundaries, and thus enhances the barrier height of grain boundaries, which are demonstrated in SEM micrographs and complex impedance. The Ca_0.5Sr_0.5Ti_0.97Sn_0.03O₃ (SnCST3) ceramics possess high energy storage density of 2.06 J/cm³ and efficiency of 95% under breakdown strength of 330 kV/cm, which get benefit from wide band gap of 5.3 eV. While the exceptional stability with minimal fluctuation (<15%) in the wide frequency range of 1–1000 Hz and temperature range of 20–120 °C are also achieved in this system. Furthermore, the pulse discharge performance are performed to appraise practical applications of pulse power capacitors. The prominent power density of 32.2 MW/cm³ and current density of 537.4 A/cm² are obtained. Meanwhile, stored energy are released in very short duration of 13 ns as well as outstanding temperature stability is realized in the temperature range of 20–120 °C for the SnCST3 ceramic, confirming it as one competitor for lead-free high power capacitors.     

Highly-reliable dielectric capacitors with excellent comprehensive energy-storage properties using Bi0.5Na0.5TiO3-based relaxor ferroelectric ceramics

The development of capacitors with high reliability and good comprehensive performances is of great significance for practical applications. In this work, lead-free relaxor ferroelectric (FE) ceramics of (1-x)(0.5(Bi_0.5Na_0.5)TiO₃-0.5SrTiO₃)-xBi(Mg_2/3Nb_1/3)O₃ ((1-x)(BNT-ST)-xBMN) were prepared by a conventional solid-state reaction method. The introduction of BMN was found to enhance local structure disorder, leading to the significantly reduced size of FE nanodomains, which is responsible for the slim polarization-electric field hysteresis loops. A giant energy-storage density of 6.62 J/cm³ and a high efficiency of 82 % can be achieved simultaneously under a moderate electric field of 34 kV/mm at x = 0.08. It also exhibits high discharge density ～ 2.74 J/cm³, large power density ～ 248 MW/cm³ and ultrafast discharge rate ～ 28 ns at 20 kV/mm in addition to excellent temperature (10–130 °C) and frequency (1–100 Hz) stabilities. These results demonstrate that the (1-x)(BNT-ST)-xBMN ceramic system is a promising lead-free candidate for advanced pulsed power capacitor applications.     

Enhanced energy storage properties in La(Mg1/2Ti1/2)O3-modified BiFeO3-BaTiO3 lead-free relaxor ferroelectric ceramics within a wide temperature range

A new ternary lead-free (0.67-x)BiFeO₃-0.33BaTiO₃-xLa(Mg_1/2Ti_1/2)O₃ ferroelectric ceramic exhibited an obvious evolution of dielectric relaxation behavior. A significantly enhanced energy-storage property was observed at room temperature, showing a good energy-storage density of 1.66 J/cm³ at 13 kV/mm and a relatively high energy-storage efficiency of 82% at x = 0.06. This was basically ascribed to the formation of a slim polarization-electric field hysteresis loop, in which a high saturated polarization P_max and a rather small remnant polarization P_r were simultaneously obtained. Particularly, its energy storage properties were found to depend weakly on frequency (0.2 Hz–100 Hz), and also to exhibit a good stability against temperature (25 °C–180 °C). The achievement of these characteristics was attributed to both a rapid response of the electric field induced reversible ergodic relaxor to long-range ferroelectric phase transition and a typical diffuse phase transformation process in the dielectric maxima.     

Excellent energy-storage performances in La2O3 doped (Na,K)NbO3-based lead-free relaxor ferroelectrics

Relaxor ferroelectric (FE) materials have received increasing attention owing to their great potentials for energy-storage applications, especially for the ones with high energy-storage density, efficiency and thermal stability simultaneously. A novel lead-free [(Na_0.5K_0.5)_0.97-xLi_0.03](Nb_0.94-xSb_0.06)O₃-xBi(Zn_1/2Zr_1/2)O₃ (NKLNS-xBZZ) ceramics was developed by a solid-state reaction method. The addition of BZZ has induced obvious dielectric relaxation behavior, as well as improved thermal stability of dielectric response. Furthermore, 0.4 wt.% La₂O₃ was added into the NKLNS-0.06BZZ ceramic, leading to an increased breakdown strength as a result of the reduction of grain size, improvement of bulk resistivity and decrease of dielectric loss. A large recoverable energy-storage density (∼4.85 J/cm³) and a high efficiency (∼88.2 %) as well as an excellent thermal stability (±12 %, 25–140 °C) were simultaneously obtained, together with a fast discharge rate (t_0.9∼112 ns). These results suggest that La₂O₃ doped NKLNS-0.06BZZ ceramic could become an attractive dielectric material for temperature-stable energy-storage capacitors.     

Simultaneously achieving high energy storage density and efficiency under low electric field in BiFeO3-based lead-free relaxor ferroelectric ceramics

BiFeO₃-BaTiO₃-based relaxor ferroelectric ceramic has attracted increasing attention for energy storage applications. However, simultaneously achieving high recoverable energy storage density (W_rec) and efficiency (η) under low electric field has been a longstanding drawback for their practical applications. Herein, a novel relaxor ferroelectric material was designed by introducing (Sr_0.7Bi_0.2)TiO₃ (SBT) into the composition 0.67BiFeO₃-0.33BaTiO₃ (BF-BT-xSBT). A large W_rec of ∼2.40 J/cm³ and a high η of ∼90.4 % were simultaneously realized under a low electric field of 180 kV/cm, which is superior to that of most previously reported lead-free ceramics. Moreover, moderate temperature endurance and excellent frequency stability were also obtained. More importantly, this ceramic has a large discharge current density (∼289.18 A/cm²), a discharge power density (∼14.46 MW/cm³) and short discharge time (<0.25 μs). These results not only demonstrate superior potential in BF-BT-SBT ceramics, but also offer a new design to tune the energy storage performance of lead-free relaxor ferroelectric ceramics.     

Enhanced breakdown strength and energy storage density in a new BiFeO3-based ternary lead-free relaxor ferroelectric ceramic

A new ternary lead-free relaxor ferroelectric ceramic of (0.67-x)BiFeO₃-0.33(Ba_0.8Sr_0.2)TiO₃-xLa(Mg_2/3Nb_1/3)O₃+y wt.% MnO₂+z wt.% BaCu(B₂O₅) (BF-BST-xLMN+y wt.% MnO₂+z wt.% BCB) was prepared by a solid-state reaction method. The substitution of LMN for BF was believed to induce a typical dielectric relaxation behavior owing to the increased random fields. After co-doping MnO₂ and BCB, a significant decrease in the conductivity and grain size was simultaneously realized, resulting in obviously enhanced dielectric breakdown strength and energy-storage performances at room temperature. A high recoverable energy storage density W˜3.38 J/cm³ and an acceptable energy storage efficiency η˜59% were achieved in the composition with x = 0.06, y = 0.1 and z = 2 under a measuring electric field of 23 kV/mm. In addition, the energy-storage performance is quite stable against both frequency (0.1 Hz–100 Hz) and temperature (30–170 °C), suggesting that BF-BST-xLMN+y wt.% MnO₂+z wt.% BCB lead-free relaxor ferroelectric ceramics might be a promising dielectric material for high-power pulsed capacitors.     

Enhanced energy storage performance in Na(1-3x)BixNb0.85Ta0.15O3 relaxor ferroelectric ceramics

High-performance lead-free dielectric containers have excellent energy storage performance such as higher power density and energy density. While being eco-friendly materials, lead-free dielectric materials are more suitable for pulse power systems than other dielectric materials. In this study, Ta⁵⁺and Bi³⁺ ions were introduced into the A site and B site of the NaNbO₃ matrix. The introduction of Bi³⁺ ions induced the formation of a vacancy in the A site, yielding Na_(1-3x)Bi_xNb_0.85Ta_0.15O₃ (NBNT, x = 0.05, 0.08, 0.11, 0.14) ceramics. The recoverable energy density (W_rec) and the energy storage efficiency (η) were highest for the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic, with values of 3.37 J/cm³ and 89% respectively. Batteries employing the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic achieved a current density of 830.4 A/cm², an energy density of 49.8 MW/cm³ and 60.2 ns discharge time. These results show that the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic is an effective energy storage material with broad application prospects.     

High energy-storage density and efficiency in PbZrO3-based antiferroelectric multilayer ceramic capacitors

The utilization of antiferroelectric (AFE) materials is commonly believed as an effective strategy to improve the energy-storage density of multilayer ceramic capacitors (MLCCs). Unfortunately, the inferior energy conversion efficiency (η) leads to high energy dissipation, which severely restricts the broader applications of MLCCs due to the increased probability of materials and/or devices failure. Herein, AFEs featuring large polarization response and small hysteresis loss are proposed to make up for deficiencies. Guided by this proposal, (Pb_0.94La_0.04)(Zr_0.69Sn_0.30Ti_0.01)O₃ AFE MLCC (abbreviated as M2) are manufactured. An ultrahigh W_rec of 16.1 J/cm³ and an excellent η of 90.9% are achieved simultaneously. Additionally, a great discharge energy density (W_dis) of 8.8 J/cm³ and a large power density (P_D) of 165.6 MW/cm³ are obtained synchronously. Noticeably, M2 exhibits excellent frequency-insensitive, temperature-bearable, and fatigue cycle-endurable energy-storage performances and/or charge-discharge properties. These results indicate that M2 has a promising prospect in advanced power electronic and/or pulsed power systems.     

Large energy storage density in BiFeO3-BaTiO3-AgNbO3 lead-free relaxor ceramics

Lead-free (0.70-x)BiFeO₃-0.30BaTiO₃-xAgNbO₃+5‰mol CuO (abbreviated as BF-BT-xAN) ceramics were fabricated using a modified thermal quenching technique. BF-BT-xAN ceramics are of a perovskite structure with morphotropic phase boundary (MPB) and show strong relaxor properties. Remarkably, the high recoverable energy storage density of 2.11 J/cm³ is obtained for BF-BT-xAN with x = 0.14. For the x = 0.14 ceramics, its energy storage efficiency is as high as 84 % at relative low field of 195 kV/cm, together with an outstanding thermal stability in a broad temperature range from 25 °C to 150 °C. In addition, this ceramic maintains superior energy storage performance even after 8 × 10⁴ electrical cycles due to its high densification after doping Ag₂O and Nb₂O₅. The result suggests that lead-free BF-BT-xAN ceramics may be promising candidate for dielectric energy storage application.     

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.     

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.     

Effect of oriented defect-dipoles on the ferroelectric and piezoelectric properties of CuO-doped (K0.48Na0.52)0.96Li0.04Nb0.805Ta0.075Sb0.12O3 ceramics

The orientation characteristics of the defect dipoles formed by acceptor ions (${\mathrm{Cu}}_{\mathrm{Nb}}^{″\prime }$) and oxygen vacancies ($V_{\mathrm{O}}^{??}$) in CuO-doped (K_0.48Na_0.52)_0.96Li_0.04Nb_0.805Ta_0.075Sb_0.12O₃ piezoceramics were investigated. The ferroelectric and piezoelectric properties of the ceramics were obviously affected by the defect dipoles which are oriented along with the domains when poled under a dc electrical field of 3.5?kV/mm at the temperature near T_C. The poled ceramics with 1.0–3.0?mol% CuO displayed strong asymmetric P-E loops and a large internal bias field (E_i), 3.89–4.57?kV/cm, when polarized at the temperature near T_C. The enhanced piezoelectric coefficient d₃₃, 186–192?pC/N, was obtained for the ceramics poled near T_C when 0.02?≤?x?≤?0.03. The ceramics with oriented defect dipoles showed a relatively good thermal stability of d₃₃ until 180?°C.     

High energy storage density realized in Bi0.5Na0.5TiO3-based relaxor ferroelectric ceramics at ultralow sintering temperature

The miniaturization and integration trend of electronic applications requires high energy storage performance, and the development of multilayer ceramic capacitors (MLCC) demands the compatibility between ceramic sintering temperature and co-firing temperature of metal electrodes. Herein, we obtained a high recoverable energy storage density and a low sintering temperature simultaneously in 0.5(Bi_0.5Na_0.5)TiO₃-0.5SrTiO₃-x mol% CuO (0.5BNT-0.5ST-x mol% CuO) via the combination of adding CuO sintering aid and citrate sol-gel synthesis method. The optimum sintering temperature decreases significantly from 1130 °C for x = 0 to 820 °C for x = 2.0. The ceramic of 0.5BNT-0.5ST-1.5 mol% CuO exhibits a large W_rec of 2.20 J/cm³ and η of 72.39% under 230 kV/cm. Furthermore, the same sample also possesses a large C_D of 1740.97 A/cm², an extremely high P_D of 139.28 MW/cm³ and an ultrafast discharge speed of 82 ns. These merits reveal that the ceramic of 0.5BNT-0.5ST-1.5 mol% CuO has great potential in practical MLCC production.     

High efficiency and power density relaxor ferroelectric Sr0.875Pb0.125TiO3- Bi(Mg0.5Zr0.5)O3 ceramics for pulsed power capacitors

Ferroelectric (1-x)Sr_0.875Pb_0.125TiO₃-xBi(Mg_0.5Zr_0.5)O₃ ((1-x)SPT-xBMZ, x = 0-0.2) ceramics with high discharge efficiency and power density were synthesized via a conventional solid-state sintering method. The prepared (1-x)SPT-xBMZ ceramics were detected as a pure perovskite structure and a dense microstructure, and a typical relaxor behavior and an excellent temperature stability were also observed. Although there is no direct correlation between the degree of diffuseness and the maximum polarization, the high degree of diffuseness can reduce the remanent polarization and significantly improve energy storage and release characteristics of ferroelectric ceramics. Based on a polarization electric-field loop measurement, a recoverable energy storage density of 0.762 J/cm³ and a very high efficiency of 96.34% are achieved when x = 0.2 under 150 kV/cm. The energy storage properties of 0.8SPT-0.2BMZ ceramic exhibit good temperature stability (25−130 °C) and frequency stability (2−80 Hz). In a practical charge-discharge circuit testing, a short discharge pulse-period about 94 ns, a high discharge energy density of 1.7 J/cm³ and an ultra-high-power density of 62.8 MW/cm³ are obtained for the 0.8SPT-0.2BMZ ceramic at 240 kV/cm. The results indicate that the 0.8SPT-0.2BMZ ceramic is a promising dielectric material for high-power pulse capacitors.     

Realizing high energy density and superior charge-discharge characteristics in NN-10BT-based ceramics

The low recoverable energy storage density (W_rec) of bulk ceramics has long limited their miniaturization and lightweight development. Here, we designed the (1-x)(0.90NaNbO₃-0.10BaTiO₃)-xNa_0.2Bi_0.4La_0.2TiO₃ (NN-10BT-xNBLT) ceramics. With the introduction of NBLT, the dielectric breakdown strength (BDS) of NN-10BT-based ceramics increased from 174.8 kV/cm to 289.1 kV/cm. A promising finding is that the NN-10BT-15NBLT ceramic has an ultrahigh energy storage density W of 3.42 J/cm³ and a large energy storage efficiency η of 78.9%, as well as excellent frequency and thermal stability. The NN-10BT-15NBLT ceramic, on the other hand, has an outstanding current density C_D of 1021.21 A/cm² together with a high power density P_D of 102.12 MW/cm³ at 200 kV/cm. Most importantly, the variation of charge-discharge properties (C_D and P_D) is only ?7.8% after 10⁴ cycles, suggesting that the capacitor has potential practical application significance.     

(1-x)Bi0.5Na0.47Li0.03TiO3-xNaNbO3 lead-free ceramics with superior energy storage performances and good temperature stability

Dielectric capacitors show great potential in superior energy storage devices. However, the energy density of these capacitors is still inadequate to meet the requirement of energy storage applications. In this study, the Bi_0.5Na_0.47Li_0.03TiO₃-xNaNbO₃ (BNLT-xNN) ceramics were prepared via conventional solid-phase reaction. Results showed that NN can efficaciously enhance the breakdown strength (E_b) and the relaxation behavior of the BNLT ceramic because of the broken ferroelectric long-range order. When x = 0.3, the maximum E_b reached 350 kV/cm, at which the 0.7BNLT-0.3NN ceramic exhibited the high recoverable energy storage density (W_rec) of 4.83 J/cm³ and great efficiency (η) of 78.9%. The ceramic demonstrated good temperature stability at 20 °C-160 °C and excellent fatigue resistance. Additionally, the 0.7BNLT-0.3NN ceramic presented high power density (P_D; ～77.58 MW/cm³), large current density (C_D; ～861.99 A/cm²), and quite short discharge time (t_0.9; ～0.090 μs). These results indicated that the 0.7BNLT-0.3NN material has excellent energy storage properties and various application prospects.     

Lead-free BaTiO3-Bi0.5Na0.5TiO3-Na0.73Bi0.09NbO3 relaxor ferroelectric ceramics for high energy storage

A series of (1-x)(0.65BaTiO₃-0.35Bi_0.5Na_0.5TiO₃)-xNa_0.73Bi_0.09NbO₃ ((1-x)BBNT-xNBN) (x = 0–0.14) ceramics were designed and fabricated using the conventional solid-state sintering method. The microstructure, dielectric property, relaxor behavior and energy storage property were systematically investigated. X-ray diffraction results reveal a pure perovskite structure and dielectric measurements exhibit a relaxor behavior for the (1-x)BBNT-xNBN ceramics. The slim polarization electric field (P-E) loops were observed in the samples with x ≥ 0.02 and the addition of Na_0.73Bi_0.09NbO₃ (NBN) could decrease the remnant polarization (P_r) of the (1-x)BBNT-xNBN ceramics obviously. The sample with x = 0.08 exhibits the highest energy storage density of 1.70 J/cm³ and the energy storage efficiency of 82% at 172 kV/cm owing to its submicron grain size and high relative density. These results show that the (1-x)BBNT-xNBN ceramics may be promising lead-free materials for high energy storage density capacitors.     

Simultaneously optimizing both energy storage density and efficiency in a novel lead-free relaxor antiferroelectrics

Dielectric capacitors with both high energy density and efficiency are highly demanded in pulsed power systems. Relaxor antiferroelectrics have attracted much attention due to their unique advantages in optimizing both properties of a dielectric capacitor. In this work, a novel relaxor antiferroelectric ceramic with composition of (1-x)Bi_0.5Na_0.5TiO₃-xAg_0.91Sm_0.03NbO₃ was developed, where the antiferroelectricity was stabilized with the increase of Ag_0.91Sm_0.03NbO₃ counterpart. Moreover, the relaxor feature was also obviously improved, as a result of chemical and structural disorder introduced by hetero cations with different radii and valence states. As expected, a high recoverable energy density of 2.1 J/cm³ accompanied with efficiency of 83 % was simultaneously achieved at x = 0.15. The as-prepared ceramics also exhibited good thermal stability in energy storage performance with small variations (energy storage density <10 % and efficiency <5 %) over 30−130 °C. All these merits demonstrate that the 0.85Bi_0.5Na_0.5TiO₃-0.15Ag_0.91Sm_0.03NbO₃ ceramic has great potential for high power energy storage applications.     

SrTiO3-modified Bi0.5Na0.47Li0.03Ti0.99Sn0.01O3 relaxor ferroelectric ceramics with high energy storage performance

(1 − x)Bi_0.5Na_0.47Li_0.03Ti_0.99Sn_0.01O₃–xSrTiO₃ (BNLST–xST) lead-free ceramics were synthesized by traditional solid phase sintering. When x = 0.4, the ceramic achieves a high energy storage density W_rec of 3.78 J/cm³ as well as a superior efficiency η of 90.3% under 360 kV/cm. The charge–discharge curves related to temperature and cycle show that the 0.6BNLST–0.4ST sample has good temperature stability (20–180°C) and cycling reliability (variation of W_D < 5%). Moreover, a fast discharge rate (t_0.9 = 0.219 μs) and a large discharge energy density (W_D = 1.89 J/cm³) are achieved at 220 kV/cm. The results show that BNLST–xST energy storage ceramics are promising materials for devices with pulsed power capacitor.     

Studies of drying and sintering characteristics of gelcast BaTiO3-based ceramic parts

Drying green gelcast parts is an essential step in the gelcasting manufacturing process. In this work, the liquid desiccant method was used for drying of BaTiO₃-based semiconducting ceramic gelcast parts. The results show that the loading level of ceramic powders and the liquid desiccant concentration significantly effect the drying process and the sintering characteristics of the ceramic parts. Lowering the loading level of ceramic powders and increasing the concentration of the liquid desiccant, non-uniform and differential drying in various regions due to great solvent gradient, induces structural and residual stresses which cause defects, such as cracking, bending and other malformations, which make the articles useless during the drying process and sintering procedure. However, when the solid loading of green gelcast parts is increased to more than 45 vol.%, the stresses developed during drying can be greatly reduced, and a higher concentration of the liquid desiccant can be used without inducing defects in the drying process and defect free ceramic with a smooth surface can be obtained. Moreover, the effects of loading level of ceramic powders and thickness of parts on the density of ceramic parts were studied. Higher solid content in the gel, and lower thickness of parts, increase the density of ceramics.