Dielectric relaxation behavior and energy storage properties in Ba0.4Sr0.6Zr0.15Ti0.85O3 ceramics with glass additives

Ba_0.4Sr_0.6Zr_0.15Ti_0.85O₃ ceramics with SrO–B₂O₃–SiO₂ glass additives were prepared via the solid state reaction route. The effects of glass contents on the sintering behavior, dielectric properties, microstructures, and energy storage properties of BSZT ceramics were investigated. Dielectric breakdown strength of 22.4 kV/mm was achieved for BSZT ceramics with 20 wt% glass addition. Dielectric relaxation behavior was observed in dielectric loss versus temperature plots. In order to investigate the mechanism of dielectric breakdown performance, the relationship between dielectric breakdown strength and grain boundary barrier was studied by the measurements of breakdown strength and activation energy. A discharged energy density of 0.45 J/cm³ with an energy efficiency of 88.2% was achieved for BSZT ceramics with 5 wt% glass addition.     

MgO-modified Sr0.7Ba0.3Nb2O6 ceramics for energy storage applications

We explored the phase structure, microstructure, dielectric and energy storage properties of MgO-modified strontium barium niobate Sr_0.7Ba_0.3Nb₂O₆-xwt%MgO (SBNMx; x?=?0–5) ceramics fabricated via conventional solid-state sintering precess. X-ray diffraction analysis indicates Mg²⁺ incorporates into lattice at x?=?0.5 and secondary phases come into formation for samples at x?≥?1, which results in the decrease of dielectric constant. There is also significant reduction of dielectric loss up to 0.002. Compared with pure SBN ceramics, the grain size of SBNMx ceramics becomes denser and more uniform, moreover, the dielectric breakdown strength shows increasing trend from 137?kV/cm to 226?kV/cm, which is in favor of the energy storage. SBNM0.5 ceramics presents the optimal energy storage performance: energy storage density of 0.93?J/cm³ and energy storage efficiency of 89.4% at 157?kV/cm, indicating that SBNM ceramics are prospective candidates for high voltage capacitor applications.     

Improvement of dielectric breakdown strength and energy storage performance in Er2O3–modified 0.95Sr0.7Ba0.3Nb2O6-0.05CaTiO3 lead-free ceramics

In this study, 0.95?Sr_0.7Ba_0.3Nb₂O₆-0.05CaTiO₃-x wt% Er₂O₃ ceramics (SBNCTEx; x?=?0–5) were synthesized using traditional solid-state method, and we investigated the microstructure, energy storage properties as well as the relationship between dielectric breakdown strength and interfacial polarization. As compared with pure 0.95?Sr_0.7Ba_0.3Nb₂O₆-0.05CaTiO₃ ceramics, the Er₂O₃ dopants suppressed the grain growth of SBNCTEx, and the doped ones showed the dense microstructure. The secondary phase was found for x?≥?1 according to the EDS results, and the influence of the secondary phase on relative dielectric breakdown strength has also been studied. The dielectric breakdown strength increased from 18.1?kV/mm to 34.4?kV/mm, which is good for energy storage. The energy storage density of 0.28?J/cm³ and the energy storage efficiency of 91.4% were obtained in the SBNCTE5 ceramics. The results indicate that SBNCTE ceramics can be used as energy storage capacitors.     

Effects of TiO2 addition on dielectric and energy storage properties of BaO-K2O-Nb2O5-SiO2 glass ceramics

In this work, 25.6BaO-6.4K₂O-32Nb₂O₅-36SiO₂-xTiO₂ (0 ≤ x ≤10 mol%) (BKNST) glass ceramics were synthesized by conventional melts and controllable crystallization method. The effects of different TiO₂ addition on the phase composition, dielectric and energy storage properties of BKNS glass ceramics were systematically evaluated. With the TiO₂ concentration increasing, a growing content of Ba₂TiO₄ phase was observed in the glass ceramics. The microstructures appeared to be homogenous and uniform with very low porosity through the addition of TiO₂, for which the maximal breakdown strength of 2112 kV/cm and the corresponding energy storage density of 9.48 J/cm³ were obtained with x = 7.5. The extremely low dielectric loss of less than 1‰ (25 °C, 100 kHz) and the obviously improved microstructure contributed to the increased breakdown strength. In addition, the discharge power density of the glass-ceramic capacitor (x = 7.5) was investigated using the RLC charge-discharge circuit and a relatively high value of 16 MW/cm³ at 300 kV/cm was obtained.     

Structural Optimization and Improved Discharged Energy Density for Niobate Glass‐Ceramics by La2O3 Addition

The structural and dielectric properties were investigated in the La₂O₃ added glass‐ceramics based on complex niobates. With the addition of La₂O₃, the optimization of microstructure was observed which resulted in the improvement of breakdown strength for the glass‐ceramics. Besides, the dielectric constant was drastically enhanced because of the doping effect of La³⁺ in the A‐sites of both crystallographic structures. Due to the combined effects of both high breakdown strength and polarization difference, the maximum discharged energy density of 1.2 J/cm³ was achieved in the niobate glass‐ceramics with 2 mol% La₂O₃, suggesting dielectric glass‐ceramics of this composition could be the most attractive candidate for high‐energy density capacitors.     

Enhanced energy storage property in glass-added Ba(Zr0.2Ti0.8)O3-0.15(Ba0.7Ca0.3)TiO3 ceramics and the charge relaxation

Glass additive BaO-SrO-TiO₂-Al₂O₃-SiO₂-BaF₂ is employed to enhance the microstructures and energy storage properties of the Ba(Zr_0.2Ti_0.8)O₃-0.15(Ba_0.7Ca_0.3)TiO₃ ceramics. To clarify the energy storage mechanism, the charge transportation and polarization process are investigated by thermally simulated depolarization current (TSDC). The dielectric breakdown strength increases from 4.3?kV/mm to 10.8?kV/mm for BZT-0.15BCT ceramics with 11?wt% glass additives, indicating that glasses could refine the grain size, uniform the structure, and decrease defects. Due to the micro-domain region, dielectric relaxation behavior is observed with a broadened and reduced dielectric constant peak at a large dielectric constant of about 3000?at room temperature. The largest charge energy density of 1.45?J/cm³ and discharge density of 0.17?J/cm³ are achieved for BZT-0.15BCT glass ceramics with 7?wt% glass additives. TSDC results demonstrate that dipole origin movement and charge transportation have an important effect on the dielectric properties and dielectric breakdown strength, respectively, which are largely influenced by the defects distribution state at the interfaces. Moderate domain walls could restrain the defects to inhibit the charge transportation and are harmful for the dielectric properties inversely. To achieve excellent energy storage performance, moderate domain walls are compromise of slightly degrading dielectric properties and greatly improving dielectric breakdown strength.     

Enhanced dielectric breakdown strength in TiO2-SiO2-Al2O3 based ceramics prepared through hot-press assisted liquid phase sintering

Linear dielectric ceramics have received much attention due to high power density, fast discharge speed and ultralow dielectric loss, which are expected as promising candidates for the pulsed power system applications. However, their relatively low dielectric breakdown strength usually cannot meet the requirements of practical application. In this work, we adopt hot-press sintering method to enhance the dielectric breakdown strength of the TiO₂-SiO₂-Al₂O₃ based ceramics, and the dielectric breakdown strength reaches 77.5 kV/mm, which is 1.8 times as large as samples prepared by conventional sintering method. The effect of different sintering methods on microstructure, dielectric properties and dielectric breakdown strength is investigated. The improvement of dielectric breakdown strength can be ascribed to improved bulk density, smaller grain size, and reduced reduction of Ti⁴⁺ to Ti³⁺, associated with the applied external pressure and lower sintering temperature. Eventually, large power density (18.20 MW/cm³) is obtained in pulse overdamped discharge circuit. Meanwhile, the stored energy is also released in a short time (about 11.3 ns to release 90% of saturated energy density value).     

Effect of sintering temperature and Ho2O3 on the properties of TiO2-based varistors

In this study, a series of TiO₂-based ceramics doped with different contents of Ho₂O₃ in the range of 0–0.6?mol% are prepared by means of a conventional solid-state reaction method. Phase composition, microstructure and element distribution are studied by use of X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) separately. The influence of sintering temperature and Ho₂O₃ on the properties of samples is explored. The results show that the breakdown voltage decreases continuously while both the nonlinear coefficient and the relative dielectric constant ascend firstly and then descend with the sintering temperature increasing. Meanwhile, the relative dielectric constant and nonlinear coefficient of samples firstly ascend and then descend with the increasing of Ho₂O₃. Although the minimum breakdown voltage (3.3?V/mm) is obtained when sample is sintered at 1450?°C, the sample doped with 0.45?mol% Ho₂O₃ sintered at 1400?°C exhibits high comprehensive electrical properties, with breakdown voltage of 6?V/mm, the nonlinear coefficient of 5.5 and the relative dielectric constant of 1.88?×?10⁵.     

Microstructure and microwave dielectric properties of Al2O3 added Li2ZnTi3O8 ceramics

Recently, the rapid development of advanced communication systems increasingly strongly demands high-performance microwave dielectric ceramics in microwave circuits. Among them, Li₂ZnTi₃O₈ ceramics have been one of the most widely investigated species, due to its high quality factor, moderate firing conditions and low cost. However, the dielectric constants of the already reported Li₂ZnTi₃O₈ ceramics are fixed in a narrow range, limiting their wider applications. To adjust the dielectric constant of the Li₂ZnTi₃O₈ based ceramics, in this work Li₂ZnTi₃O₈ ceramics added with different amounts of Al₂O₃ (0–8?wt%) were prepared by conventional solid-state reaction. The microstructure and microwave dielectric properties of the samples were investigated. Due to the addition of Al₂O₃, the sintering temperature of the ceramics would be increased somewhat. Some Al³⁺ ions could substitute for Ti⁴⁺ ions in Li₂ZnTi₃O₈, and the added Al₂O₃ would react with ZnO to produce a ZnAl₂O₄ phase accompanying with the formation of TiO₂ phase, which would inhibit the growth of Li₂ZnTi₃O₈ grains. The dielectric constant of the finally obtained ceramics would be reduced from 26.2 to 17.9, although the quality factors of the obtained ceramics would decrease somewhat and the temperature coefficient of resonant frequency would deviate further from zero.     

Enhanced energy storage and fast discharge properties of BaTiO3 based ceramics modified by Bi(Mg1/2Zr1/2)O3

Lead-free (1-x)BaTiO₃-xBi(Mg_1/2Zr_1/2)O₃ ((1-x)BT-xBMZ) ceramics with perovskite structure were synthesized by solid-state reaction methods. (1-x)BT-xBMZ solid solution transforms from tetragonal (x≤0.04) to pseudocubic (x≥0.08) and exhibits a dispersive dielectric behavior with respect to frequency, showing typical relaxor characteristics with BMZ increasing. The optimal energy storage density of 1.25 J cm^?3 and energy efficiency of >95% are obtained at x = 0.15, with maximum dielectric breakdown strength of 185 kV cm^-1 at 200 μm thickness., The energy storage density and energy efficiency of 0.85BT-0.15BMZ ceramics maintain at about 0.8 J cm^?3 and 89% at 150 kV cm^-1 over temperature range of 25 °C～150 °C, exhibiting good thermal stability. The pulse discharge capability of 0.85BT-0.15BMZ ceramics were measured under different electric fields, showing a short charge-discharge time of 1.3 μs. Therefore (1-x)BT-xBMZ solid solution with high energy density and efficiency, good temperature stability and fast discharge speed, is promising candidate for high power applications.     

Low-temperature preparation and microwave dielectric properties of cold sintered Li2Mg3TiO6 nanocrystalline ceramics

This study aims to fabricate Li₂Mg₃TiO₆ ceramics with ultrafine grains using a novel cold sintering process combined with a post-annealing treatment at a temperature <?950?°C. In this study, phase composition, sintering behavior, microstructure evolution, and microwave dielectric properties of the resultant nanocrystalline ceramics were investigated for the first time. The as-compacted green pellets at 180?°C yielded a high relative density of ~ 90% and the ceramics that were post-sintered over a broad temperature range (800–950?°C) possessed highly dense microstructure with a relative density of ~ 96%. The average grain size varied from 100 to 1200?nm for the samples sintered at 800–950?°C. Furthermore, the quality (Q × f) values of the obtained specimens exhibited a strong positive dependency on the grain size, which increased from 17,790 to 47,960?GHz for grain sizes ranging between 100 and 1200?nm, while the dielectric permittivity (ε_r) and temperature coefficient of the resonant frequency (τ_f) values did not undergo any significant changes over this range of grain size.     

Significantly enhanced energy‐storage density in the strontium barium niobate‐based/titanate‐based glass‐ceramics

Two‐step crystallization process was employed to improve microstructure and energy‐storage density of the strontium barium niobate‐based/titanate‐based glass‐ceramics. By using two‐step crystallization process, the optimum nucleation temperature was obtained to improve dielectric breakdown strength. Compared to the breakdown strength by one‐step crystallization process, the breakdown strength by two‐step crystallization process is increased about 1.89 times with the optimum nucleation temperature. Energy‐storage density of 7.73 ± 0.26 J/cm³ is significantly improved by two‐step crystallization process and is about 2.9 times of 2.63 ± 0.17 J/cm³ by one‐step crystallization process. This result is attributed to the homogeneous nucleation improving the microstructures of glass‐ceramics. Identification and quantification of crystalline phases by using Rietveld refinement reveals the difference of dielectric constants for one‐step and two‐step crystallization processes.     

Effects of phase constitution and microstructure on energy storage properties of barium strontium titanate ceramics

Barium strontium titanate (Ba_0.3Sr_0.7TiO₃, BST) ceramics have been prepared by conventional sintering (CS) and spark plasma sintering (SPS). The effects of phase constitution and microstructure on dielectric properties, electrical breakdown process and energy storage properties of the BST ceramics were investigated. The X-ray diffraction analysis and dielectric properties measurements showed that the cubic and tetragonal phase coexisted in the SPS sample while the CS sample contained only tetragonal phase. Much smaller grain size, lower porosity, fewer defects and dislocation were observed in SPS samples, which greatly improved the electrical breakdown strength of the Ba_0.3Sr_0.7TiO₃ ceramics. The enhanced breakdown strength of the SPS samples resulted in an improved maximum electrical energy storage density of 1.13 J/cm³ which was twice as large as that of the CS sample (0.57 J/cm³). Meanwhile, the energy storage efficiency was improved from 69.3% to 86.8% by using spark plasma sintering.     

Crystal structure,microwave dielectric properties and low temperature sintering of (Al0.5Nb0.5)4+ co-substitution for Ti4+ of LiNb0.6Ti0.5O3 ceramics

The phase composition, microstructure, microwave dielectric properties of (Al_0.5Nb_0.5)⁴⁺ co-substitution for Ti site in LiNb_0.6Ti_0.5O₃ ceramics and the low temperature sintering behaviors of Li₂O-B₂O₃-SiO₂ (LBS) glass were systematically discussed. XRD patterns and EDS analysis result confirmed that single phase of Li_1.075Nb_0.625Ti_0.45O₃ solid solution was formed in all component. The increase of dielectric constant (ε_r) is ascribed to the improvement of bulk density. The restricted growth of grain has a negative influence on quality factor (Q×f) value. The τ_f value could be continuously shifted to near zero as the doping content increases. Great microwave dielectric properties were obtained in LiNb_0.6Ti_(0.5-x)(Al_0.5Nb_0.5)_xO₃ ceramics (x?=?0.10) when sintered at 1100?℃ for 2?h: ε_r =?70.34, Q×f =?5144?GHz, τ_f =?4.8?ppm/℃. The sintering aid, LBS glass, can effectively reduce the temperature and remain satisfied microwave performance. Excellent microwave dielectric properties for x?=?0.10 were obtained with 1.0?wt% glass: ε_r =?70.16, Q×f =?4153?GHz (at 4?GHz), τ_f =?-0.65?ppm/℃ when sintered at 925?℃ for 2?h.     

Improved dielectric strength and energy storage density in Ba6−3xLa8+2xTi18O54 (x = 0.5, 2/3, and 0.75) ceramics

Dielectric strength and energy storage density in Ba_6−3xLa_8+2xTi₁₈O₅₄ (x = 0.5, 2/3, and 0.75) ceramics were investigated as functions of composition and microstructure. With increasing x, although the dielectric constant decreased from 113 to 102, the energy storage density increased from 2.3 J/cm³ to 3.2 J/cm³ due to the increased dielectric strength for ceramics prepared by conventional sintering. The energy storage was further improved to 4.2 J/cm³ in ceramics prepared by spark plasma sintering under an electric field of 1058 kV/cm. Both dielectric strength and energy storage density in the present ceramics indicated the strong processing and microstructure dependence. The optimum dielectric strength and energy storage density were achieved in the dense ceramics with fine grains, while both dielectric strength and energy storage density decreased in the ceramics with coarse columnar grains.     

Composition-dependent xBa(Zr0.2Ti0.8)O3-(1-x)(Ba0.7Ca0.3)TiO3 bulk ceramics for high energy storage applications

This work reports the composition dependent microstructure, dielectric, ferroelectric and energy storage properties, and the phase transitions sequence of lead free xBa(Zr_0.2Ti_0.8)O₃-(1-x)(Ba_0.7Ca_0.3)TiO₃ [xBZT-(1-x)BCT] ceramics, with x?=?0.4, 0.5 and 0.6, prepared by solid state reaction method. The XRD and Raman scattering results confirm the coexistence of rhombohedral and tetragonal phases at room temperature (RT). The temperature dependence of Raman scattering spectra, dielectric permittivity and polarization points a first phase transition from ferroelectric rhombohedral phase to ferroelectric tetragonal phase at a temperature (T_R-T) of 40?°C and a second phase transition from ferroelectric tetragonal phase - paraelectric pseudocubic phase at a temperature (T_T-C) of 110?°C. The dielectric analysis suggests that the phase transition at T_T-C is of diffusive type and the BZT-BCT ceramics are a relaxor type ferroelectric materials. The composition induced variation in the temperature dependence of dielectric losses was correlated with full width half maxima (FWHM) of A₁, E(LO) Raman mode. The saturation polarization (P_s) ≈8.3?μC/cm² and coercive fields ≈2.9?kV/cm were found to be optimum at composition x?=?0.6 and is attributed to grain size effect. It is also shown that BZT-BCT ceramics exhibit a fatigue free response up to 10⁵ cycles. The effect of a.c. electric field amplitude and temperature on energy storage density and storage efficiency is also discussed. The presence of high T_T-C (110?°C), a high dielectric constant (ε_r ≈?12,285) with low dielectric loss (0.03), good polarization (P_s ≈?8.3?μC/cm²) and large recoverable energy density (W?=?121?mJ/cm³) with an energy storage efficiency (η) of 70% at an electric field of 25?kV/cm in 0.6BZT-0.4BCT ceramics make them suitable candidates for energy storage capacitor applications.     

Microwave dielectric ceramics in (Mg1/3Sb2/3)O2-ZrO2-TiO2 system with near zero τf and low loss in a very wide range

A series of (ZrTi)_1-x(Mg_1/3Sb_2/3)_2xO₄ (0.04?≤?x?≤?0.36) ceramics were successfully synthesized through the conventional solid-state processing. Appropriate content of CuO was added as sintering aids to promote the density of ceramics. The XRD analysis revealed that the main crystalline phase of ceramics sintered at optimal temperature belonged to α-PbO₂-type structure. Raman spectroscopy and far infrared reflectivity (FIR) spectra were employed to study the phonon modes of ceramics, which explained the relationship between microwave dielectric properties and structure. It is interesting that the τ_f are near-zero (+6.6 ~ ?4.6?ppm/°C) and meanwhile the Q×f are relatively high (29,000–41,800?GHz) for samples with x in a very wide range of 0.10–0.36. In this range, their dielectric constants (ε_r) can be adjustable from 35.4 to 24.4. The results demonstrated this ceramic system is a potential candidate for microwave dielectric applications requiring an adjustable dielectric constants and near zero τ_f.     

Effects of Li2O-B2O3-SiO2 glass on the low-temperature sintering of Zn0.15Nb0.3Ti0.55O2 ceramics

The influences of Li₂O-B₂O₃-SiO₂ glass (LBS) on the activation energy, phase composition, the stability of the structure and microwave dielectric properties of Zn_0.15Nb_0.3Ti_0.55O₂ ceramics have been systematically investigated. LBS glass acted as flux former and contributed to the reactive liquid-phase sintering mechanism, which remarkably lowed the sintering temperature from 1150?°C to 900?°C and enhanced the shrinkage and densification of ceramic at the low sintering temperatures. The ceramics with 1.5?wt% LBS glass sintered at 900?°C for 3?h show great properties: ε_r = 73.59, Q × f = 8024?GHz, τ_f = 270.54?ppm/°C.     

Energy storage properties of NaNbO3-CaZrO3 ceramics with coexistence of ferroelectric and antiferroelectric phases

Anti-ferroelectric materials with large saturated polarization, small remnant polarization, and moderate breakdown strength are receiving increasing attention for modern high-power electrical systems. Here we demonstrated that by incorporating CaZrO₃ into NaNbO₃ ceramics, the antiferroelectricity in NaNbO₃-CaZrO₃ solid solutions could be stabilized at room temperature. The effects of phase constitution and microstructure on the dielectric properties, electrical breakdown strength, and energy storage properties of the NaNbO₃-CaZrO₃ ceramics were investigated. Ferroelectric and antiferroelectric phase coexistence in the NaNbO3-CaZrO₃ was confirmed by XRD and TEM analyses. With increasing CaZrO₃ content, the grain size was reduced, and the dielectric breakdown strength was improved. Therefore, a high energy density of 0.55?J/cm³ and efficiency of 63% was obtained in the NaNbO₃-0.04CaZrO₃ ceramics. These lead-free NaNbO₃-CaZrO₃ antiferroelectrics with good electrical energy storage can be exploited for high-power storage devices.     

Energy storage density and tunable dielectric properties of BaTi0.85Sn0.15O3/MgO composite ceramics prepared by SPS

(100-x) wt.% BaTi_0.85Sn_0.15O₃–x wt.% MgO (BTS/MgO) composite ceramics were prepared by spark plasma sintering (SPS) technology. Phase constitution, microstructure, dielectric and electrical energy storage properties of BTS/MgO composite ceramics were investigated. The samples prepared by SPS had smaller grain size and presented layer-plate substructure. Dielectric permittivity and dielectric loss of BTS/MgO composite ceramics decreased significantly with the content of MgO increasing, and dielectric tunability maintained a relatively high value (>45%). Meanwhile, the dielectric breakdown strength was improved when addition of MgO in BTS matrix, which resulted in a significant improvement of energy storage density. The high dielectric breakdown strength of 190 kV/cm, energy storage density of 0.5107 J/cm³ and energy storage efficiency of 92.11% were obtained in 90 wt.% BaTi_0.85Sn_0.15O₃–10 wt.% MgO composite ceramics. Therefore, BTS/MgO composites with good tunable dielectric properties and electrical energy storage properties could be exploited for energy storage and phase shifter device applications.