Excellent thermal stability and energy storage properties of lead-free Bi0.5Na0.5TiO3-based ceramic

The ceramic capacitors with excellent energy storage properties and wide operating temperature are the main challenges in power system applications. Here, the lead-free (1-x)Bi_0.5Na_0.5TiO₃-xCaTiO₃ (abbreviated as BNT-xCT) ceramics were synthesized through solid-state reaction method. The introduction of CT reduced the temperature of permittivity peak of BNT ceramic, guaranteeing excellent thermal stability over a wide temperature range of −100 ∼ 136°C. Meanwhile, the long-range order structure of BNT was destructed by structural distortion, and the relaxor behavior was enhanced after doping CT. Moreover, the direct current breakdown strength was improved from 203 to 455 kV/cm, and the high recoverable energy density (W_rec ∼ 2.74 J/cm³) with high efficiency (η ∼ 91%) was achieved for BNT-0.25CT ceramic, along with a fast discharge speed (t_0.9 ∼ 110 ns) superior cycle stability and thermal stability. Those properties enabled a promising practical prospect of BNT-CT ceramics.     

“Dark hole” cure in Ba4.2Nd9.2Ti18O54 microwave dielectric ceramics

Large size Ba_4.2Nd_9.2Ti₁₈O₅₄ (BNT) ceramics doped with MnCO₃, CuO and CoO were prepared by the conventional solid-state method. Only a single BaNd₂Ti₄O₁₂ phase was formed in all samples. No second phase was found in the XRD patterns. The bulk density increases slightly because of the dopants. The SEM results showed that the grain size of Mn²⁺and Cu²⁺-doped BNT ceramics became larger with the increasing amount of dopants. The permittivity of all samples stays the same. However, the Q×f value of BNT ceramics increases by doping, especially with Mn²⁺ ions. The conductivity of BNT ceramic doped with Mn²⁺(0.5 mol‰) under high temperature is lower than that without doping. There are fewer defects in Mn²⁺-doped BNT ceramics. The XPS results indicated that Ti reduction was suppressed in BNT ceramics doped with 0.5 mol‰ Mn²⁺. BNT ceramics doped with 0.5 mol‰ Mn²⁺ ions sintered at 1320 °C for 2 h exhibited good microwave dielectric properties, with ε_r=88.67, Q×f=7408 GHz and τf = 82.98 ppm/°C.     

Enhanced energy density and thermal stability in relaxor ferroelectric Bi0.5Na0.5TiO3-Sr0.7Bi0.2TiO3 ceramics

Sr_0.7Bi_0.2TiO₃ (SBT) was introduced into Bi_0.5Na_0.5TiO₃ (BNT) via a standard solid-state route to modulate its relaxation behaviour and energy storage performance. With increasing SBT content, the perovskite structure of BNT transforms from a rhombohedral phase to a weakly polarized pseudo-cubic phase, and the relaxation behaviour is enhanced. In particular, the E_DBS is improved from 120 kV/cm of BNT to 160 kV/cm of 0.6BNT-0.4SBT, which displays a large recoverable energy storage density (W_rec = 2.20 J/cm³), implying a large potential ability of energy storage for the 0.6BNT-0.4SBT ceramic. Moreover, both dielectric properties (28–326 °C) and energy storage properties (20–140 °C) exhibit a good thermal stability for the same 0.6BNT-0.4SBT composition. These characteristics suggest 0.6BNT-0.4SBT ceramic could be a promising candidate to be applied in a pulse power system over a broad temperature range.     

Fabrication of Lu2O3:Eu transparent ceramics using powder consisting of mono-dispersed spheres

Mono-dispersed spherical Lu₂O₃:Eu (5 mol%) powders for transparent ceramics fabrication were synthesized by urea-based homogeneous precipitation technique. The effects of the doped-Eu³⁺ on the synthesis of Lu₂O₃:Eu particles were investigated in detail. The results show that the doping of Eu³⁺ ions into Lu system can significantly decrease the particle size of the resultant precursor spheres. Owing to the sequential precipitation in Lu/Eu system, there are compositional gradients within each of the resultant precursor spheres. Well dispersed, homogeneous and spherical/near spherical Lu₂O₃:Eu powders were obtained after calcination at 600–1000 °C for 4 h. The powder calcined at 600 °C shows better sintering behavior and can be densified into transparent ceramic after vacuum sintering at 1700 °C for 5 h. The luminescence properties of the obtained Lu₂O₃:Eu powder and transparent ceramic were also studied.     

High-temperature dielectric and relaxation behavior of Yb-doped Bi0.5Na0.5TiO3 ceramics

Microstructure, phase transition and dielectric properties of Yb-doped Bi_0.5Na_0.5TiO₃ (BNT) ceramics were investigated. It is found that ytterbium promotes the grain growth and densification of the ceramics while Ti-rich impurity appears due to the compensation of Ti-vacancy. The dielectric operational temperature range of the ceramics with a±15% tolerance was greatly broaden until 500 °C by ytterbium doping. Meanwhile, the diffuseness of the diffuse phase transition increases with the increase of doping Yb. BNT ceramics with 3 mol% Yb doping shows a near-plateau dielectric behavior in a broad temperature range from 147 to 528 °C and a low dielectric loss (<0.025) from 154 to 356 °C, indicating that it is a promising material for applications in high-temperature capacitor.     

Lead-reduced Bi(Ni2/3Ta1/3)O3-PbTiO3 perovskite ceramics with high Curie temperature and performance

With increasing demand of high-temperature piezoelectric devices and growing concern over environment protection, a feasible reduction in lead from lead-based high Curie temperature piezoelectric materials are desperately needed. Herein, a new system of lead-reduced Bi(Ni_2/3Ta_1/3)O₃-PbTiO₃ (BNT-PT) ferroelectric ceramics is fabricated by a conventional solid-state sintering process. The phase transition behaviors as a function of composition and temperature, electrical properties, as well as the domain configurations from a microscopic level have been investigated in detail. The results indicate that crystal structures, phase transition behaviors, and electric properties of BNT-PT ceramics can be affected significantly by the content of BNT counterpart. Dielectric measurements show that xBNT-(1−x)PT ceramics transfer from the normal ferroelectrics to the relaxor ferroelectrics at compositions of x = 0.3-0.35. The BNT-PT ceramics exhibit high Curie temperature T_C ranging from 474 to 185°C with the variation in BNT content. The relative dielectric tunability n_r also rises from only 0.65% for 0.10BNT-0.90PT to 50.23% for 0.40BNT-0.60PT with increasing BNT content. The tetragonal-rich composition 0.30BNT-0.70PT ceramic possesses the maximum remnant polarization of P_r ~ 34.9 μC/cm². Meanwhile, a highest piezoelectric coefficient of d₃₃ ~ 271 pC/N and a high field piezoelectric strain coefficient of  ~ 560 pm/V are achieved at morphotropic phase boundary (MPB) composition of 0.38BNT-0.62PT. The maximum value of strain ~0.31% is obtained in the 0.36BNT-0.64PT ceramic. The largest electromechanical coupling coefficient k_p is 44.5% for 0.37BNT-0.63PT ceramic. These findings demonstrate that BNT-PT ceramics are a system of high-performance Pb-reduced ferro/piezoelectrics, which will be very promising materials for piezoelectric devices. This study offers an approach to developing and exploring new lead-reduced ferroelectric ceramics with high performances.     

Enhanced insulating and piezoelectric properties of BiFeO3-BaTiO3-Bi0.5Na0.5TiO3 ceramics with high Curie temperature

BiFeO₃-BaTiO₃ ceramics are promising lead-free piezoelectric ceramics due to their high piezoelectric properties and high Curie temperature, but their high leakage current density makes the poling difficult. In this study, a decreased leakage current density by three orders of magnitude was obtained in Bi_0.5Na_0.5TiO₃ (BNT) added 0.67BiFeO₃-0.33BaTiO₃ (BF-BT) ceramics. It was found that the largely improved insulating properties benefit from the reduced oxygen vacancies and weak reduction of Fe³⁺ to Fe²⁺ as confirmed by photoluminescence and X-ray photoelectron spectroscopy measurements, thereby contributing to high-temperature and high-field poling. In addition, the introduction of BNT leaded to increased grain size. Due to the grown grains as well as reduced oxygen vacancies and Fe²⁺, enhanced insulating and optimal piezoelectric properties with P_r = 24.2 µC/cm², d₃₃ = 183 pC/N, k_p = 0.28, and T_C = 467°C were achieved in BF-BT-0.05BNT ceramics.     

Preparation and photoluminescence properties of Eu3+-doped ZrO2 nanotube arrays

Zr–Eu alloy containing 3 at% Eu was prepared by a powder metallurgical method and Eu³⁺-doped ZrO₂ nanotube arrays were prepared by anodising the Zr–Eu alloy. The properties of Eu³⁺-doped ZrO₂ nanotube arrays were studied in contrast to undoped ZrO₂ nanotube arrays under different annealing temperatures. Results showed that the Eu³⁺ ions could not only stabilise the tetragonal phase of zirconium oxide, but also make the crystallite sizes smaller. Annealing temperature exerted a significant influence on the absorbance value, as well as the intensity and position of the photoluminescence peaks. When the excitation wavelength was either 248 nm or 270 nm, the sample annealed at 600 °C displayed the strongest emission peak; while under excitation at 232 nm, the sample annealed at 400 °C exhibited the strongest emission peak.     

Studies of dielectric properties of rare earth (Dy,Tb, Eu) doped barium titanate sintered in pure nitrogen

This paper investigated dielectric properties of rare earth (Dy, Tb, Eu)-doped barium titanate sintered in pure nitrogen. The substituting concentration of rare earth (Dy, Tb, Eu) was 2.0 mol%. The doping behaviors of intermediate rare-earth ions (Dy, Tb, Eu) and their effects on the dielectric property of barium titanate were investigated. Eu³⁺ ion was substituted in the A-site of the perovskite lattice. Dy³⁺ and Tb³⁺ ions substituted partially for Ti⁴⁺ site and partially for Ba²⁺ site. The different rare earth element had a crucial effect on dielectric properties of rare-earth-doped BaTiO₃. Among these doped samples, Tb-doped BaTiO₃ had the largest dielectric constant (70,000–80,000); the smallest dielectric loss (less than 4%), and good capacitance-temperature coefficient, which satisfies the X7R specification of the Electronic Industries Association Standards (TCC within ±15% from ?55 °C to 125 °C).     

Preparation and Electric Properties of Bi0.5Na0.5TiO3–Bi(Al0.5Ga0.5)O3 Lead‐Free Piezoceramics

A new lead‐free BNT‐based piezoelectric ceramics of (1 ? x)Bi_0.5Na_0.5TiO₃–xBi(Al_0.5Ga_0.5)O₃ (x = 0, 0.02, 0.03, 0.04, and 0.05) were synthesized using a conventional ceramic fabrication method. Their structures and electrical properties were investigated. All the samples show a typical ferroelectric P(E) loops and S(E) curves at room temperature. The optimal properties are obtained at the composition of the x = 0.03. The substitution of Bi(Al_0.5Ga_0.5)O₃ enhances piezoelectric constant and increases Curie temperature from 58 pC/N and 310°C of pure BNT to 93 pC/N and 325°C of the x = 0.03. The temperature‐dependent P(E) loops and S(E) curves of 0.97BNT–0.03BAG indicate that phase transition from ferroelectric to antiferroelectric takes place over a very wide temperature region from 80°C to 180°C. The results show that the introduction of BAG improves the electrical properties of BNT.     

Dielectric temperature stability of Nb-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

In this study, the phase structure, microstructure and dielectric properties of Bi_0.5(Na_0.78K_0.22)_0.5(Ti_1-xNb_x)O₃ lead-free ceramics prepared by traditional solid phase sintering method were studied. The second phase pyrochlore bismuth titanate (Bi₂Ti₂O₇) was produced in the system after introduction of Nb⁵⁺. The dielectric constant of the sample (x = 0.03) sintered at 1130 °C at room temperature reached a maximum of 1841, and the dielectric loss was 0.045 minimum. It had been found that the K⁺ and Nb⁵⁺ co-doped Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics exhibited outstanding dielectric-temperature stability within 100–400 °C with T_cc ≤±15%. Result of this research provides a valuable reference for application of BNT based capacitors in high temperature field.     

High permittivity and excellent high-temperature energy storage properties of X9R BaTiO3–(Bi0.5Na0.5)TiO3 ceramics

We fabricated x(Bi_0.5Na_0.5)TiO₃–(1−x)[BaTiO₃–(Bi_0.5Na_0.5)TiO₃–Nb] (BNT-doped BTBNT-Nb) dielectric materials with high permittivity and excellent high-temperature energy storage properties. The initial powder of Nb-modified BTBNT was first calcined and then modified with different stoichiometric ratios of (Bi_0.5Na_0.5)TiO₃ (BNT). Variable-temperature X-ray diffraction (XRD) results showed that the ceramics with a small amount of BNT doping consisted of coexisting tetragonal and pseudocubic phases, which transformed into the pseudocubic phase as the test temperature increased. The results of transmission electron microscopy (TEM) showed that the ceramic grain was the core-shell structure. The permittivity of the 5 mol% BNT-doped BTBNT-Nb ceramic reached up to 2343, meeting the X9R specification. The discharge energy densities of all samples were 1.70-1.91 J/cm³ at room temperature. The discharge energy densities of all samples fluctuated by only ±5% over the wide temperature range from 25°C to 175°C and ±8% from 25°C to 200°C. The discharge energy density of the 50 mol% BNT-doped BTBNT-Nb ceramic was 2.01 J/cm³ at 210 kV/cm and 175°C. The maximum energy efficiencies of all ceramics were up to ~91% at high temperatures and were much better than those at room temperature. The stable dielectric properties within a wide temperature window and excellent high-temperature energy storage properties of this BNT-doped BTBNT-Nb system make it promising to provide candidate materials for multilayer ceramic capacitor applications.     

Enhanced optical transmittance and energy-storage performance in NaNbO3-modified Bi0.5Na0.5TiO3 ceramics

Dielectric ceramics with both excellent energy storage and optical transmittance have attracted much attention in recent years. However, the transparent Pb-free energy-storage ceramics were rare reported. In this work, we prepared transparent relaxor ferroelectric ceramics (1 − x)Bi_0.5Na_0.5TiO₃–xNaNbO₃ (BNT–xNN) by conventional solid-state reaction method. We find the NN-doping can enhance the polarization and breakdown strength of BNT by suppressing the grain growth and restrained the reduction of Ti⁴⁺ to Ti³⁺. As a result, a high recoverable energy-storage density of 5.14 J/cm³ and its energy efficiency of 79.65% are achieved in BNT–0.5NN ceramic at 286 kV/cm. Furthermore, NN-doping can promote the densification to improve the optical transmittance of BNT, rising from ∼26% (x = 0.2) to ∼32% (x = 0.5) in the visible light region. These characteristics demonstrate the potential application of BNT–xNN as transparent energy-storage dielectric ceramics.     

Electrical properties and temperature stability of SrTiO3-modified (Bi1/2Na1/2)TiO3-BaTiO3-(K1/2Na1/2)NbO3 piezoceramics

SrTiO₃-modified lead-free piezoelectric ceramics, (0.93-x)Bi_0.5Na_0.5TiO₃-xSrTiO₃-0.06BaTiO₃-0.01 K_0.5Na_0.5NbO₃ [(BNT-xST)-BT-KNN, x = 0-0.06], were prepared using a conventional solid-state reaction method. The XRD structure analysis and electric properties characteristics revealed the ST-induced phase transformation from the ferroelectric phase to the relaxor phase and their coexistence state. Benefiting from the ST-destructed ferroelectric long-range orders, the high normalized strain value of 600 pm/V was obtained in the (BNT-0.02ST)-BT-KNN ceramic at 5 kV/mm. The ST-generated relaxor phase was found to have a constructive effect on improving the temperature stability and restraining the hysteresis of the electric-field-induced strain. The normalized strain of (BNT-0.06ST)-BT-KNN ceramics could be kept at a high value ~337 pm/V at elevated temperature up to 120°C.     

Ferroelectric photovoltaic and flexo-photovoltaic effects in (1 − x)(Bi0.5Na0.5)TiO3-xBiFeO3 systems under visible light

The anomalous photovoltaic (APV) effect has witnessed great progress from classical ferroelectric photovoltaics to flexo-photovoltaics. Both call for an extension of the spectral response range. Here, we present a comprehensive study on the ferroelectric, photoelectric, and photovoltaic properties of pure (Bi_0.5Na_0.5)TiO₃ (BNT) and 0.3(Bi_0.5Na_0.5)TiO₃–0.7BiFeO₃ (0.3BNT-0.7BFO) ceramics. The data show that pure BNT with typical ferroelectricity exhibits intriguing photovoltaic effect even when illuminated by 550 nm visible light, while the 0.3BNT-0.7BFO solid solution with enhanced visible light absorption shows no ferroelectric photovoltaic due to the negligible ferroelectricity but striking strain-induced flexo-photovoltaic effect. Transmission electron microscopy analysis reveals distinctions in the domain structures and local strain states in pure BNT and 0.3BNT-0.7BFO ceramics, which may account for their differences in photovoltaic behavior. These findings not only deepen the understanding of photovoltaic mechanisms induced by ferroelectric polarization and flexoelectric effect but also highlight a possible candidate for multifunctional photoelectric applications.     

Structural,dielectric and luminescent properties of novel Li1.0Nb0.6Ti0.5O3: Tb3+ ceramics

Novel Li_1.0Nb_0.6Ti_0.5O₃: Tb³⁺ ceramics with favorable luminescent and dielectric properties were prepared by solid-state reaction (SSR) method. The X-ray diffraction (XRD) results indicated that the Tb³⁺ ions were effectively dissolved into the “M-phase” matrix synthesized at 1000–1100°C. The ceramic with a dense microstructure could be obtained at 1050°C. The Li_1.0Nb_0.6Ti_0.5O₃: Tb³⁺ ceramics emitted green light at 550 nm and relatively strong red light at 660 nm under the excitation of 440 nm, which were located in the orange-red light region shown in the chromaticity diagram. The color coordinates were (0.5574, 0.4417) for the Li_1.0Nb_0.6Ti_0.5O₃: 2wt% Tb³⁺ ceramic sintered at 1050°C. The quantum efficiency of Li_1.0Nb_0.6Ti_0.5O₃: 2wt%Tb³⁺ ceramic was 19%, which was much higher than that of 9.6% for commercial red Y₂O₃: Eu³⁺ phosphors. Furthermore, for Li_1.0Nb_0.6Ti_0.5O₃: 2wt%Tb³⁺ ceramic synthesized at 1050°C, the ideal dielectric properties with ε_r of 66.263 and Q*f of 5582 GHz were obtained, which might be used as a potentially multifunctional ceramic applied in the fields of LED packaging to improve the lack of red light for blue LEDs combined with yellow phosphors.     

Achieving excellent energy storage properties of Na0.5Bi0.5TiO3 - based ceramics by using a two-step strategy involving phase and polarization modification

Na_0.5Bi_0.5TiO₃-based ceramic specimens have been extensively investigated as ferroelectric materials. After being doped with CaTiO₃, the resulting Na_0.5Bi_0.5TiO₃-based ceramics exhibit relaxor characteristics, and improved energy storage density and efficiency. Based on these above results, CeO₂ was further employed to modify the polarization of the 0.85Na_0.5Bi_0.5TiO₃-0.15CaTiO₃ matrix ceramic to achieve better energy storage performance. The effective energy storage density was enhanced from 1.93 to 2.53 J/cm³ by using the appropriate doping concentration of CeO₂. Grain refinement effect can effectively enhance the electric-field strength from approximately 190 to 230 kV/cm. In particular, when doped with 2% CeO₂, the energy storage efficiency of the sample was maintained at approximately 90% at 30 °C-150 °C and at approximately 80% in the frequency range of 0.2–200 Hz. This combination has very excellent temperature stability and frequency stability, making it a promising candidate for energy storage applications.     

Effects of Nb-doping on the micro-structure and dielectric properties of (Bi0.5Na0.5)TiO3 ceramics

Bismuth sodium titanate [(Bi_0.5Na_0.5)TiO₃ or BNT] ceramics incorporated with 0, 1, 5, 10, 15 and 20 mol% niobium were prepared by conventional solid state reaction method. The green bodies were sintered at 1050 °C for 2 h to obtain dense ceramics. The effects of substitution of niobium ion for titanium ion in BNT ceramics on micro-structure and dielectric properties were investigated. X-ray diffraction analysis showed the presence of a secondary phase when more than 5 mol% niobium was added. Within the solubility limit, Nb doping caused the grain size of BNTNb to be smaller than the undoped sample. The investigation of the dielectric properties showed that the transition temperature (T_c) was found to shift towards lower temperature as the content of Nb increased. In this research, the donor-type behavior and induced charged defects had significant influence on the electrical properties of Nb-doped BNT ceramics.     

Effects of Gd Substitution on Sintering and Optical Properties of Highly Transparent (Y0.95−xGdxEu0.05)2O3 Ceramics

Highly transparent (Y_0.95?xGd_xEu_0.05)₂O₃ (x = 0.15–0.55) ceramics have been fabricated by vacuum sintering at the relatively low temperature of 1700°C for 4 h with the in‐line transmittances of 73.6%–79.5% at the Eu³⁺ emission wavelength of 613 nm (~91.9%–99.3% of the theoretical transmittance of Y_1.34Gd_0.6Eu_0.06O₃ single crystal), whereas the x = 0.65 ceramic undergoes a phase transformation at 1650°C and has a transparency of 53.4% at the lower sintering temperature of 1625°C. The effects of Gd³⁺ substitution for Y³⁺ on the particle characteristics, sintering kinetics, and optical performances of the materials were systematically studied. The results show that (1) calcining the layered rare‐earth hydroxide precursors of the ternary Y–Gd–Eu system yielded rounded oxide particles with greatly reduced hard agglomeration and the particle/crystallite size slightly decreases along with increasing Gd³⁺ incorporation; (2) in the temperature range 1100°C–1480°C, the sintering kinetics of (Y_0.95?xGd_xEu_0.05)₂O₃ is mainly controlled by grain‐boundary diffusion with similar activation energies of ~230 kJ/mol; (3) Gd³⁺ addition promotes grain growth and densification in the temperature range 1100°C–1400°C; (4) the bandgap energies of the (Y_0.95?xGd_xEu_0.05)₂O₃ ceramics generally decrease with increasing x; however, they are much lower than those of the oxide powders; (5) both the oxide powders and the transparent ceramics exhibit the typical red emission of Eu³⁺ at ~613 nm (the ⁵D₀→⁷F₂ transition) under charge transfer (CT) excitation. Gd³⁺ incorporation enhances the photoluminescence and shortens the fluorescence lifetime of Eu³⁺.     

Effect of B2O3 on the sintering and microwave dielectric properties of M-phase LiNb0.6Ti0.5O3 ceramics

The effect of B₂O₃ addition on the sintering, microstructure and the microwave dielectric properties of LiNb_0.6Ti_0.5O₃ ceramics have been investigated. It is found that low-level doping of B₂O₃ (≤2 wt.%) can significantly improve the densification and dielectric properties of LiNb_0.6Ti_0.5O₃ ceramics. Due to the liquid phase effect of B₂O₃ addition, LiNb_0.6Ti_0.5O₃ ceramics could be sintered to a theoretical density higher than 95% even at 880 °C. No secondary phase was observed for the B₂O₃-doped ceramics. There is no obvious degradation in dielectric properties for the ceramics with B₂O₃ additions. In the case of 1 wt.% B₂O₃ addition, the ceramics sintered at 880 °C show good microwave dielectric properties of ɛ_r = 70, Q × f = 5400 GHz, τ_f = −6.39 ppm/°C. It represents that the ceramics could be promising for multilayer low-temperature co-fired ceramics (LTCC) applications.