Enhancing the dielectric and energy storage properties of lead-free Na0.5Bi0.5TiO3–BaTiO3 ceramics by adding K0.5Na0.5NbO3 ferroelectric

A novel strategy of enhancing the dielectric and energy storage properties of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) ceramics by introducing a K_0.5Na_0.5NbO₃ (KNN) ferroelectric phase is proposed herein, and its underlying mechanism is elucidated. The lead-free KNN ceramic decreases the residual polarisation and increases the electric breakdown strength of the NBT–BT matrix through the simultaneous modification of its A-sites and B-sites. The obtained NBT?BT?x?KNN ceramics have a perovskite structure with unifying grains. A bulk 0.9NBT–BT–0.1KNN ceramic sample with a thickness of 0.2 mm possesses a high energy storage density of 2.81 J/cm³ at an applied electric field of 180 kV/cm. Moreover, it exhibits good insulation properties and undergoes rapid charge and discharge processes. Therefore, the obtained 0.9NBT–BT–0.1KNN ceramic can be potentially used in high-power applications because of its high energy density, good insulation properties, and large discharge rate.     

Enhanced energy storage properties of BiAlO3 modified Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3 lead-free antiferroelectric ceramics

Lead-free (1−x)(0.75Bi_0.5Na_0.5TiO₃–0.25Bi_0.5K_0.5TiO₃)–xBiAlO₃ (BNT–BKT–100xBA, x=0–0.10) ceramics were prepared by two-step sintering method and their phase structure, micro morphology and electrical properties were systematically investigated. X-ray diffraction analysis indicates a pure perovskite phase for x≤0.06 as well as a structural evolution from a tetragonal toward a pseudocubic phase. Transmission electron microscopy study of the x=0.04 composition reveals the existence of antiferroelectric phase with a⁰a⁰c⁺ oxygen octahedron tilting which is in the form of nano-domains. Polarization-electric field and current-electric field hysteresis loops demonstrate that the increase of BA concentration destroys the ferroelectric order and strengthens antiferroelectric order. A much enhanced energy storage density of 1.15 J/cm³ and efficiency of 73.2% is achieved under 105 kV/cm at x=0.06. In addition, its energy storage property is found to depend weakly on temperature within the measurement range of 25–150 °C.     

Phase transition and energy storage properties of Bi0.5Na0.5TiO3–Bi(Mg2/3Nb1/3)O3 lead-free ceramics

Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics have been extensively studied due to their excellent dielectric, piezoelectric and ferroelectric properties. The phase structure and functionalities of BNT can be feasibly adjusted by doping/forming solid solutions with other elements/components. In this work, Bi(Mg_2/3Nb_1/3)O₃ (BMN) was introduced into BNT by a conventional solid-state reaction to form a homogeneous solid solution of (1-x)(Bi_0.5Na_0.5)TiO₃-xBi(Mg_2/3Nb_1/3)O₃ (BNT-xBMN) with a perovskite structure. With the increase of BMN content, a phase transition from rhombohedral R3c to tetragonal P4bm has been confirmed by XRD, along with shifting the ferroelectric-paraelectric phase transition temperature to lower temperatures with broadening dielectric peaks. Furthermore, an optimized recoverable energy density of 1.405 J/cm³ was achieved for BNT-0.10BMN ceramics under a low applied electric field of 140 kV/cm, which is mainly attributed to the transformation from ferroelectric to ergodic relaxor phase.     

The electrical properties of (1−x)(Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–BaTiO3)–xCaZrO3 lead-free piezoelectric ceramics

Lead-free (1−x)(0.0852Bi_0.5Na_0.5TiO₃–0.12Bi_0.5K_0.5TiO₃–0.028BaTiO₃)–xCaZrO₃ piezoelectric ceramics (BNT−BKT−BT−xCZ, x=0, 0.01, 0.02, 0.03, 0.04 and 0.05) were prepared by using a conventional solid-state reaction method. The effects of CZ-doping on the structural, dielectric, ferroelectric and piezoelectric properties of the BNT−BKT−BT−xCZ system were systematically investigated. The polarization and strain behaviors indicated that the long-range ferroelectric order in the unmodified BNT−BKT−BT ceramics was disrupted by the increase of CZ-doping content, and correspondingly the depolarization temperature (T_d) shifted down from 109 °C to below room temperature. When x>0.03, accompanied with the drastic decrease in the remnant polarization (P_r) and piezoelectric coefficient (d₃₃), the electric-field-induced strain was enhanced significantly. A large unipolar strain of 0.35% under an applied electric field of 70 kV/cm (S_max/E_max=500 pm/V) was obtained in the BNT−BKT−BT−0.04CZ ceramics at room temperature, which was attributed to the reversible electric-field-induced phase transition between the relaxor and ferroelectric phases.     

Effect of WO3 doping on dielectric and ferroelectric properties of 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 ceramics

WO₃(0–6 mol%)-doped 0.94Bi_0.5Na_0.5TiO₃–0.06BaTiO₃ lead-free ceramics were synthesized by conventional solid-state reaction. The effect of WO₃ addition on the structure and electrical properties were investigated. The result revealed that a small amount of WO₃ (≤1 mol%) can diffuse into the lattice and does not significantly affect the phase structure, however, more addition will result in distortion and enlargement of the unit cells. The maximum permittivity temperature (T_m) is suppressed dramatically as the dopant increasing, while the depolarization temperature (T_d) fall to the minimum with 1 mol% WO₃ additive. The remanent polarization (P_r) was enhanced and coercive field (E_c) was reduced by doping with WO₃. The strain shows the largest value for 1 mol% doped sample, which is due to a field-induced antiferroelectric–ferroelectric phase transition.     

Enhanced dielectric energy storage performance of A-site Ca2+-doped Na0.5Bi0.5TiO3–BaTiO3–BiFeO3 Pb-free ceramics

(1-x) (0.98Na_0.5Bi_0.5TiO₃–0.01BaTiO₃–0.01BiFeO₃)–xCaTiO₃ (NBB-xCT) ceramics were produced using traditional solid-state synthesis methods. The surface morphology, domain structure, and electrical properties of the ceramic samples were systematically studied. In addition, the temperature and frequency stabilities of the NBB-15CT sample at 200 kV/cm were tested. Generally, NBB-xCT ceramics exhibit a typical single perovskite phase structure. The results indicate that the NBB-15CT ceramics showed a high energy density of 3.14 J/cm³ at 250 kV/cm. The piezoresponse force microscopy (PFM) results showed that the addition of CT broke the macrodomains of the 0.98Na_0.5Bi_0.5TiO₃-0.01BaTiO₃-0.01BiFeO₃ ceramic and helped to form nanodomains, leading to an improved energy storage performance. The above performance indicates that the specimens possess very good temperature-and frequency-dependent energy storage performances at 30–150 °C and 1–100 Hz. Moreover, the electric energy storage and release in the NBB-15CT ceramic indicated that the power density could reach 55.30 MV/cm³ at 180 kV/cm. Therefore, the NBB-15CT ceramic is a promising material for electrical capacitors.     

Ferroelectric properties and large electric field-induced strain of Eu3+-doped Na0.5Bi0.5TiO3–BaTiO3 lead-free ceramics

Eu³⁺-doped lead-free piezoelectric ceramics, 0.937Na_0.5Bi_0.5?xEu_xTiO₃-0.063BaTiO₃ (abbreviated as NBE_xT-BT, where x = 0, 0.003, 0.005, 0.01, 0.013, 0.015, 0.017, and 0.02), were synthesized using a conventional solid-state synthesis method. All the component samples were crystallized in a pure perovskite structure without a secondary phase. The introduction of Eu³⁺ caused the evident variation of the dielectric, ferroelectric and luminescence properties. The remanent polarization and coercive field of the pure NBT-BT are P_r ～29.24 μC/cm², E_c～39.33 kV/cm, respectively. The maximum of the remanent polarization P_r of ～38.02 μC/cm² at room temperature and the highest dielectric constant of 6899 with a frequency of 1 kHz were obtained for NBE_0.003T-BT. The maximum bipolar strain S_max of ～0.91% and the minimum of coercive field E_c ～18.45 kV/cm were achieved by the NBE_0.015T-BT, resulting from the formation of a double hysteresis loop. For all the components, Eu³⁺ doping stabilized the antiferroelectric phenomenon at high temperature. Furthermore, the polarized NBE_0.015T-BT had the strongest fluorescence luminescence intensity as well as a fluorescence lifetime reaching 785.98 μs.     

Optimized piezoelectric and structural properties of (Bi,Na)TiO3–(Bi,K)TiO3 ceramics for energy harvester applications

We investigated (1−x)(Bi,Na)TiO₃–x(Bi,K)TiO₃ (x=0, 0.14, 0.16, 0.18, 0.20, and 0.22) compositions of lead-free piezoelectric ceramics for potential energy harvester applications. Composition and sintering temperature of (1−x)(Bi,Na)TiO₃–x(Bi,K)TiO₃ were varied to extract the optimized processing temperature with each composition. We compared and analyzed sintering temperature-dependent surface morphologies and electrical properties. Maximum piezoelectric charge constant of 180 pC/N were obtained from the 0.8(Bi,Na)TiO₃–0.2(Bi,K)TiO₃composition at the sintering temperature of 1180 °C. Temperature dependent dielectric permittivity was measured to know the phase transition. We corresponded two different anomaly peaks, observed at 84 and 290 °C, as the rhombohedral-tetragonal and tetragonal-cubic phase transitions, respectively. Due to these phase transitions, different shapes of polarization-electric field loops (P-E loops) were measured and compared. Finally, output power of 42.39 nW/cm² were obtained for the (1−x)(Bi,Na)TiO₃–x(Bi,K)TiO₃ lead free piezoelectric ceramics.     

An effective optimization strategy and analysis for BaTiO3–Na0.5Bi0.5TiO3 system with colossal permittivity

Colossal permittivity (CP, ε＞10⁴) behavior in BaTiO₃–Na_0.5Bi_0.5TiO₃ (BT-NBT) ceramics has been studied, which showed extremely high permittivity up to ~10⁵. Dielectric properties of samples showed Debye-like relaxations in the frequency range 20 Hz–30 MHz. Two different polarizations located in grain boundaries and grains respectively are responsible for the CP behavior and the models of defect charge compensation achieved by niobium doping are proposed to explain the phenomenon of abnormal variation of dielectric constant.By using defect engineering, a Nb-doped BaTiO₃ ceramics with stable colossal permittivity (ε_r =1.3×10⁴ at 1 kHz and room temperature),high bulk resistivity (>10¹⁰ Ω·cm) as well as relative low dielectric loss (tanδ~0.06) has been obtained over a wide temperature range of −55–150 °C, satisfying IEA X8R specification, which has a potential application prospect in high capacity solid supercapacitor.     

High energy storage efficiency and fast discharge property of temperature stabilized Ba0.4Sr0.6TiO3–Bi(Mg0.5Ti0.5)O3 ceramics

(1?x)Ba_0.4Sr_0.6TiO₃-xBi(Mg_0.5Ti_0.5)O₃ ((1?x)BST-xBMT) relaxor ferroelectric ceramics were prepared by a conventional solid-state method. In this work, the microstructure, dielectric properties, and pulsed charge–discharge properties were investigated. The doping of BMT caused a decrease in the surface energy and grain boundary energy, and contributed to the formation of polar nanoregions (PNRs). The existence of PNRs was confirmed by piezoresponse force microscopy measurements (PFM) on the 0.8BST-0.2BMT ceramic. The PNRs responded quickly under an AC voltage, thus the pulsed charge–discharge time was short (<80 ns), aiming to realize time compression to improve the power density (P_D). The PNRs were not closely connected to each other and adverse to the formation of leakage current and pinning, thus inhibiting charge transfer at the grain boundaries and contributing to the high energy storage efficiency (η ～ 93%). In addition, the 0.8BST-0.2BMT ceramic also displayed excellent temperature stability. The capacitance-temperature dependence satisfied the requirement of X8R (?55–150 °C, ΔC/C_{25 °C} ≤ ±15%), and η had no obvious fluctuation in the temperature range from 25 °C to 150 °C. This study could provide a successful method to achieve a temperature stable and high η, and a fast charge–discharge process.     

Novel NaNbO3–Sr0.7Bi0·2TiO3 lead-free dielectric ceramics with excellent energy storage properties

NaNbO₃ (NN) is considered to be one of the most prospective lead-free antiferroelectric energy storage materials due to the merits of low cost, nontoxicity, and low density. Nevertheless, the electric field-induced ferroelectric phase remains dominant after the removal of the electric field, resulting in large residual polarization, which prevents NN ceramics from obtaining superior energy storage performance. In this work, the relaxor ferroelectric Sr_0·7Bi_0·2TiO₃ (SBT) was chosen to partially replace the NN ceramics, and the introduction of the nanodomain of the relaxor ferroelectric hinders the generation of field-induced ferroelectric phases, allowing the material to combine the large polarization strength of the relaxor ferroelectric with the near-zero residual polarization of the antiferroelectric. Large recoverable energy storage density (4.5 J cm^?3) and ultra-high energy storage efficiency (90.3%) were gained in NN-20SBT under an electric field of 288 kV cm^?1. Furthermore, superior temperature (25–120 °C) and frequency (1–500 Hz) stabilities were acquired. These performances demonstrate that NN-20SBT ceramics are potential candidates as dielectric materials for high energy storage density pulsed power capacitors.     

Phase–composition and temperature dependence of electrocaloric effect in lead–free Bi0.5Na0.5TiO3–BaTiO3–(Sr0.7Bi0.2□0.1)TiO3 ceramics

The (0.94–x)Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–x(Sr_0.7Bi_0.2□_0.1)TiO₃ (BNT–BT–xSBT, 0 ≤ x ≤ 0.24) solid solution ceramics were synthesized via a conventional solid–state reaction method and the correlation of phase structure, piezoelectric, ferroelectric properties and electrocaloric effect (ECE) was investigated in detail. The ECE in lead–free BNT–BT–xSBT ceramics was measured directly using a home–made adiabatic calorimeter with maximum adiabatic temperature change ΔT = 0.4 K with x = 0.08 under the electric field E = 6 kV/mm at room temperature. The position of maximum ECE was found in the vicinity of nonergodic and ergodic phase boundary, where the maximum change in entropy occurs as a result of the field–induced phase transformation between the ergodic and long–range ferroelectric phase. Besides, the mechanism for the shift of ECE peak is discussed in detail. Finally, the temperature dependence of ECE for BNT–BT–xSBT (x = 0, 0.04 and 0.08) was also investigated. This work may present a guideline for designing BNT–based ferroelectric relaxor ceramics for EC cooling technologies.     

Influence of sintering temperature on energy storage properties of BaTiO3–(Sr1−1.5xBix) TiO3 ceramics

The effect of sintering temperature on microstructure, dielectric properties and energy storage properties of BaTiO₃–(Sr_1?1.5xBi_x)TiO₃ (x = 0.09) (BT–SBT) ceramics was investigated. The sintering temperature has pronounced influence on the grain size, shrinkage, and dielectric properties of the BT–SBT ceramics. With increasing sintering temperature, the dielectric constant increases largely. However, the increasing tendency of the dielectric breakdown strength (BDS) is less noticeable but become more evident with the consideration of Weibull modulus. For the BT-SBT ceramics, the unreleased energy density decreases and the electric field stability of the energy storage efficiency enhances with the increase of sintering temperature.     

Thermal and dynamic mechanical analyses on Bi0.5Na0.5TiO3–BaTiO3 ceramics synthesized with citrate method

Bi_0.5Na_0.5TiO₃–xBaTiO₃ (BNT–xBT) nano-powders are successfully synthesized by a modified citrate method. The as-prepared BNT-BT powders and the sintered ceramics are homogeneous with a pure perovskite crystal structure. The effects of Ba²⁺ substitutions for (Bi_0.5Na_0.5)²⁺ in the A-sites of Bi_0.5Na_0.5TiO₃ on its phase transformations are explored. The transformations among ferroelectric (FE), anti-ferroelectric (AFE) and paraelectric (PE) states in these ceramics are characterized using ferroelectric hysteresis tests, modulated differential scanning calorimetry and dynamic mechanical analysis. The FE-AFE transition in BNT–xBT with 0≤x≤0.15 is found to relate with a structural transformation which is a first-order phase transition. The mechanical and thermal analyses provide evidence that AFE state (0≤x≤0.15) could be associated with the incommensurate modulation of rhombohedral structures while the mechanisms of forming AFE state in BNT–xBT (x>0.15) could be different.     

Structure,dielectric and ferroelectric properties of 0.92Na0.5Bi0.5TiO3–0.06BaTiO3–0.02K0.5Na0.5NbO3 lead-free ceramics: Effect of Co2O3 additive

0.92Na_0.5Bi_0.5TiO₃–0.06BaTiO₃–0.02K_0.5Na_0.5NbO₃+x wt% Co₂O₃ (NBKT–xCo, x=0, 0.2, 0.4, 0.6, 0.8) lead-free ferroelectric ceramics were prepared via a conventional solid state reaction method. Effects of Co₂O₃ additive on crystallite structure, microstructure, dielectric and ferroelectric properties of the NBKT–xCo ceramics were studied. X-ray diffraction results showed that the rhombohedral–tetragonal morphotropic phase boundary existed in all the ceramics, with relative amount of tetragonal phase varying with the content of Co₂O₃. Average grain size, maximum value of dielectric constant, Curie temperature and ferroelectric properties of the ceramics were close related to the content of Co₂O₃. The dielectric anomaly caused by the phase transition between the ferroelectric phase and the so-called “intermediate phase” was observed in the ceramics with x≤0.2, while it disappeared with further increasing x. All the ceramics showed a diffuse phase transition between the “intermediate phase” and the paraelectric phase. The change in the ferroelectric properties with changing the content of Co₂O₃ was discussed by considering the competitive effects among grain size, relative amount of the tetragonal phase and oxygen vacancies.     

Electrocaloric effect and pyroelectric energy harvesting of (0.94 − x)Na0.5Bi0.5TiO3-0.06BaTiO3-xSrTiO3 ceramics

Ceramics with the composition (0.94 − x)Na_0.5Bi_0.5TiO₃–0.06BaTiO₃–xSrTiO₃ (NBBSTx) where x = 0.10, 0.15, 0.20, and 0.25 were synthesized by a conventional solid-state reaction method to investigate their electrocaloric effect (ECE) and pyroelectric energy harvesting (PEH) properties. The ferroelectric, dielectric, and pyroelectric properties of the prepared ceramics were measured and discussed. It is found that the strontium titanate (ST) content and bias field greatly affect the ferroelectric–relaxor transition. Increasing ST content lowers the depolarization temperature of the ceramics, and both the ECE and PEH behavior of the ceramics strongly depend on their ST content because of the composition-induced decrease of the ferroelectric–relaxor transition temperature. The present investigation demonstrates that the ECE and PEH properties of NBBSTx ceramics can be tuned by introducing ST. Furthermore, a high PEH density of 425 kJ/m³ is obtained for NBBST0.20, which is much higher than those of conventional Pb-based ferroelectrics.     

Energy storage properties of MgO-doped 0.5Bi0·5Na0·5TiO3-0.5SrTiO3 ceramics

0.5Bi_0·5Na_0·5TiO₃-0.5SrTiO₃-x wt% MgO (x = 0, 0.5, 1.0, 1.5, 2.0, 3.0) ceramics were fabricated via solid-state method. The effect of MgO doped on energy storage properties, dielectric performance, phase structure and microstructures of 0.5Bi_0·5Na_0·5TiO₃-0.5SrTiO₃ (BNST) ceramics were studied systemically. The Mg²⁺ substituted Ti⁴⁺ site in BNST, which was confirmed by X-ray diffraction (XRD) result. The scanning electron microscope (SEM) images show that all the ceramic samples exhibit uniform and compact morphologies. The temperature dependent permittivity exhibits frequency dispersion, indicating that the ceramic samples are typical relaxor ferroelectrics. It was found that MgO doped BNST can significant improve the breakdown strength (E_b) of samples from 109 kV/cm to 227 kV/cm, which results in a great enhancement on energy storage density. The sample of x = 3.0 has the largest energy storage density (2.17 J/cm³), which is twice as much as the BNST. Consequently, we consider that MgO-doped BNST ceramics are able to be a promising candidate in the field of pulsed-power devices.     

Dielectric,ferroelectric, and depolarization properties of B-site manganese-doped 0.925(Bi0.5Na0.5)TiO3–0.075BaTiO3 solid solutions

(Bi_0.5Na_0.5)_0.925Ba_0.075(Ti_1−xMn_x)O₃ (x=0, 0.2, 1.0, and 2.0 mol%) ceramics were prepared by solid-state-reaction method to study dielectric, ferroelectric, and depolarization properties. The manganese (Mn) doping can suppress dielectric permittivity and increase relaxor behavior. Coercive field (E_c) increases, while remanent polarization (P_r) decreases as the Mn content increases. P_r exhibits discontinuous anomalies as a function of temperature in all compositions, implying a polarization reorganization of local domains. The depolarization temperature (T_d) reaches the highest value (~152 °C) in 0.2%Mn, and decreases as MnO₂ content increases. The increased T_d in 0.2%Mn is due to two-phase coexistence and structural thermal stability induced by Mn ions. This work suggests that the moderate Mn doping can enhance T_d in lead-free piezoceramics for applications at elevated temperatures.