Giant field-induced strain in Nb2O5-modified (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

Lead-free piezoceramics (Na_(1+x)/2Bi_(1-x)/2)_0.94Ba_0.06Ti_1-xNb_xO₃ (BTN100x) were prepared using conventional solid-state reaction method. The structures, field- induced strain, AC impedance of sintered ceramics were investigated. The pure perovskite solid solution BTN3 exhibited giant electric-field-induced strain of 0.478% under an electric field of 70 kV/cm at ambient temperature, meanwhile, the normalized strain (S_max/E_max) reached up to 654 pm/V. The giant strain was insensitive to temperature and exhibited excellent fatigue resistance performance within 10⁶ switching cycles, making it a promising candidate material for actuator applications. Complex AC impedance spectra confirmed the contribution of grain effect to resistivity behavior. The field-induced giant strain was attributed to the phase transition between ferroelectrics and relaxor ferroelectrics induced by introducing Nb₂O₅.     

Polarization behavior of` lead-free 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 thin films with enhanced ferroelectric properties

(Bi_0.5Na_0.5)TiO₃ based ferroelectric lead-free thin films have great potential for modern micro-devices. However, the multicomponent feature and volatile nature of Bi/Na makes the achievement of high quality films challenging. In this work, the morphotropic phase boundary composition, 0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ thin films were successfully prepared by CSD method. Dense films with low dielectric loss and low leakage current density were obtained. A well-defined polarization hysteresis loop with a high remnant polarization was observed in the thin films. Moreover, the polarization behavior of the film at original state, under electric field and upon heating was investigated by PFM. A self-polarization and asymmetric domain switching behavior were observed. High temperature induced depolarization and the self-polarization recovered upon cooling. The thin films with good quality show a promising potential for the application in electrical devices, and the in-depth investigation of the polarization behavior improves the understanding of ferroelectric and piezoelectric properties of thin films.     

Enhanced temperature stable dielectric properties and energy-storage density of BaSnO3-modified (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

A series of (1-x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃-xBaSnO₃ (BNBT-100xBSN, x = 0–20) lead-free ceramics were synthesized using a conventional high-temperature solid-state reaction route. The effects of BaSnO₃ on the dielectric, ferroelectric and energy-storage performance of BNBT-BSN were systematically investigated. Temperature dependent permittivity curves indicated the obviously enhanced relaxor ferroelectric property. The introduction of BaSnO₃ reduced the temperature corresponding to the first dielectric anomaly, which facilitated the dielectric temperature stability. △ε'/ε'_150°C varied no more than 15% within the temperature range of up to 338 °C (45–383 °C) for BNBT-15BSN. A slimed P-E loop was obtained with the remnant polarization of 0.4 μC/cm² for BNBT-15BSN. Moreover, the breakdown field intensity of BNBT-BSN increased effectively from 80 kV/cm to 115 kV/cm. Therefore, an optimum energy-storage performance was obtained in BNBT-15BSN with the energy-storage density of 1.2 J/cm³ whose energy-storage efficiency reached 86.7%. Furthermore, the possible contributions of defect and vacancy to relaxation and conductance mechanism were discussed by studying the impedance and electric modulus. The results above indicated the BNBT-100xBSN be a promising lead-free candidate for energy-storage capacitors.     

Large field-induced strain with enhanced temperature-stable dielectric properties of AgNbO3-modified (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(1-x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃-xAgNbO₃ lead-free piezoelectric ceramics (abbreviated as BNBT-100xAN) were prepared using the conventional solid-state sintering method. The effects of the introduction of AgNbO₃ (AN) dopants for the dielectric and piezoelectric performances of BNBT-100xAN ceramics were systematically studied. The XRD patterns and Raman spectra demonstrated that AN as a modifier was successfully diffused into the BNBT-100xAN lattice and revealed a pseudo-cubic symmetry structure. All samples exhibited a dense surface morphology accompanied by the uniform distribution of elements. A large bipolar strain of ~0.501% and unipolar strain of ~0.481% corresponding to the normalized strain d₃₃* of ~740 p.m./V were achieved for BNBT-1AN ceramic at 65 kV/cm field. The BNBT-4AN ceramic exhibited an excellent temperature-stable permittivity with the range from 59 to 380 °C and its dielectric loss was less than 0.02 between 97 °C and 329 °C. These results revealed that BNBT-100xAN ceramics were more hopeful candidates for actuators, strain sensors, and high-temperature capacitors.     

Enhanced energy storage performance in Sn doped Sr0.6(Na0.5Bi0.5)0.4TiO3 lead-free relaxor ferroelectric ceramics

SnO₂ doped Sr_0.6(Na_0.5Bi_0.5)_0.4TiO₃ (NBT-ST) ceramics were prepared by a conventional solid-state reaction method. Their phase structures, microstructures and electrical properties were characterized in details. It is found that SnO₂ doping could increase the lattice parameters, density and average grain size. A suitable amount of SnO₂ can improve dielectric properties, and affect the relaxor behavior of the NBT-ST matrix, thereby it can effectively reduce the energy loss and optimize the energy storage performance. Furthermore, the energy storage properties are improved with SnO₂ doping. Especially, the 1 at. % SnO₂ doped NBT-ST achieves a high recoverable energy density of 2.35 J/cm³, which is mainly attributed to large maximum polarization of 43.2 μC/cm², small remnant polarization of 5.83 μC/cm² and high breakdown strength of 180 kV/cm. Also, relatively good temperature stability for dielectric performance and excellent fatigue resistance are observed in this composition. These properties are attractive for lead-free energy storage applications.     

Giant electric field-induced strain at room temperature in LiNbO3-doped 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3

We report experimental investigation on the ferroelectricity and electric field-induced strain response in LiNbO₃-doped 0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ (BNT-BT) piezoelectric ceramics. At room temperature, a large strain of 0.6% (at 70 kV/cm) is achieved in the 2.5%-LiNbO₃-doped BNT-BT, higher than that of commercially-utilized Pb(Zr,Ti)O₃. The corresponding piezoelectric coefficient d^*₃₃ reaches 857 pm/V, which is high among these of BNT-based ceramics at room temperature. Further study indicates that the superior piezoelectric properties are realized at the ferroelectric-relaxor transition temperature T_F-R, which is pushed to room temperature with 2.5% LiNbO₃ doping. This indicates that large electromechanical response can be induced via delicate mixing of the ferroelectric rhombohedral phase and the polar nanoregions (PNRs) relaxor-ferroelectric tetragonal phase.     

Enhancement of pyroelectric properties of lead-free 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 ceramics by La doping

Lead-free 0.94NBT-0.06BT-xLa ceramics at x = 0.0–1.0 (%) were synthesized by a conventional solid-state route. XRD shows that the compositions are at a morphotropic phase boundary where rhombohedral and tetragonal phases coexist. With increasing La³⁺ content pyroelectric coefficient (p) and figures of merits greatly increase; however, the depolarization temperature (T_d) decreases. p is 7.24 × 10⁻⁴C m⁻² °C⁻¹ at RT at x = 0.5% and 105.4 × 10⁻⁴C.m^−2 °C⁻¹ at T_d at x = 0.2%. F_i and F_v show improvements at RT from 1.12 (x = 0%) to 2.65 (x10 ⁻¹⁰ m v⁻¹) (x = 0.5%) and from 0.021 to 0.048 (m².C⁻¹) respectively. F_i and F_v show a huge increase to 37.6 × 10⁻¹⁰ m v⁻¹ and 0.56 m² C⁻¹ respectively at T_d at x = 0.2%. F_C shows values of 2.10, 2.89, and 2.98 (x10⁻⁹C cm⁻² °C⁻¹) at RT at 33, 100 and 1000 (Hz) respectively. Giant pyroelectric properties make NBT-0.06BT-xLa at x = 0.2% and 0.5% promising materials for many pyroelectric applications.     

The effects of aliovalent cations doping on electric-field-induced strain and microstructures of (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free piezoceramics

Effects of Al and Nb doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃(abbreviated as BNB6T) ceramics on dielectric, ferroelectric, and strain properties were investigated. The results indicated that the d₃₃^? value is significantly higher in pure BNB6T ceramics than in Nb doped BNB6T and Al doped BNB6T ceramics, and that S–E curve for the Al doped BNB6T ceramics displayed a typical W-shaped butterfly curve, but pure BNB6T and Nb doped BNB6T ceramics display a V-shaped curve. The P–E loops for pure BNB6T and Nb doped BNB6T ceramics were similar to soft PZT ceramics with slim profiles. According to the results of microstructures analysis, significant strain may originate from the development of the optimum compound domains coexistence (the mixture of microdomain and nanodomain), which provide large saturation polarization and low-energy barrier dipole switching under an applied electric field. All these would provide a new concept for lead-free ceramics to realize high strain response for practical applications in actuator or other piezoelectric devices.     

Electric-field-temperature phase diagram and electromechanical properties in lead-free (Na0.5Bi0.5)TiO3-based incipient piezoelectric ceramics

In this work, the (1-x)(0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃)-xSrTiO₃ (NKBT-xST) incipient piezoelectric ceramics with x = 0–0.07 (0ST-7ST) were prepared by the solid-state reaction method and their structural transformation and electromechanical properties were investigated as a function of ST content. As the ST content increases, the long-range ferroelectric order is disrupted, and the ferroelectric-relaxor phase transition temperature (T_FR) shifts to around room temperature for NKBT-5ST ceramics, accompanied by a relatively high electrostrain of 0.3% at 6 kV/mm. The large strain response associated with the vanished ferroelectric properties around T_FR can be attributed to the reversible relaxor-ferroelectric phase transition. The electric-field-temperature (E-T) phase diagrams were established, and the transition between the two field-induced long-range ferroelectric states were found to take place via a two-step switching process through an intermediate relaxor state. The threshold electric field to trigger the conversion between ferroelectric state and relaxor state depends strongly on the dynamics of polarization relaxation, which is influenced by temperature and composition.     

Enhanced pyroelectric response from domain-engineered lead-free (K0.5Bi0.5TiO3-BaTiO3)-Na0.5Bi0.5TiO3 ferroelectric ceramics

Enhanced pyroelectric response is achieved via domain engineering from [001] grain-oriented, tetragonal-phase, lead-free 0.2(2/3K_0.5Bi_0.5TiO₃-1/3BaTiO₃)-0.8Na_0.5Bi_0.5TiO₃ (KBT-BT-NBT) ceramics prepared by a templated grain growth method. The [001] crystallographic orientation leads to large polarization in tetragonal symmetry; therefore, texturing along this direction is employed to enhance the pyroelectricity. X-ray diffraction analysis revealed a Lotgering factor (degree of texturing) of 93 % along the [001] crystallographic direction. The textured KBT-BT-NBT lead-free ceramics showed comparable pyroelectric figures of merit to those of lead-based ferroelectric materials at room temperature (RT). In addition to the enhanced pyroelectric response at RT, an enormous enhancement in the pyroelectric response (from 1750 to 90,900 μC m^?2 K^?1) was achieved at the depolarization temperature because of the sharp ferroelectric to antiferroelectric phase transition owing to coherent 180° domain switching. These results will motivate the development of a wide range of lead-free pyroelectric devices, such as thermal sensors and infra-red detectors.     

Large electro-strain with excellent fatigue resistance of lead-free (Bi0.5Na0.5)0.94Ba0.06Ti1-x(Y0.5Nb0.5)xO3 perovskite ceramics

A series of lead-free (Bi_0.5Na_0.5)_0.94Ba_0.06Ti_1-x(Y_0.5Nb_0.5)_xO₃ (for 0 ≤ x ≤ 0.03) perovskite ceramics were fabricated using a solid-state reaction technique. The effects of (Y_0.5Nb_0.5)⁴⁺ ions doping on phase structure, piezoelectric properties, AC impedance, and fatigue resistance were systematically studied. Crystal structure as a function of the composition revealed a single perovskite lattice structure with dense micromorphology. The transition temperature of the non-ergodic and ergodic relaxor ferroelectric phase shifted to near ambient temperature with increasing composition, which was related to the destruction of the long-range ordered ferroelectric domains. Hence, the transformation of ferroelectric-to-relaxor phase was easier under applied electric field at room temperature. The ceramic for x = 0.01 composition attained a large unipolar strain of ~ 0.452% with a corresponding normalized strain (d₃₃*) of ~ 603 pm/V under applied 75 kV/cm field. Besides, the excellent fatigue resistance of the sample was obtained after 10⁵ switching cycles under 70 kV/cm. These phenomena demonstrated that (Bi_0.5Na_0.5)_0.94Ba_0.06Ti_1-x(Y_0.5Nb_0.5)_xO₃ ceramics might be suitable for a wide range of electronic equipment applications such as actuators and sensors.     

Nanoscale origins of small hysteresis and remnant strain in Bi0.5Na0.5TiO3-based lead-free ceramics

BiAlO₃-doped Bi_0.5Na_0.5TiO₃-Bi_0.5K_0.5TiO₃ (BA-doped BNT-BKT) ceramics are greatly concerned due to their sufficient electric-field-induced strain with small hysteresis and remnant strain for high precision positioning devices and other actuators. In this paper, the structural analysis especially the high-resolution transmission electron microscope (HRTEM) is used to reveal the origin of excellent properties obtained in 0.96(0.75BNT-0.25BKT)-0.04BA, which exhibits a large strain of 0.21% at ～70 kV/cm, a small strain hysteresis of only 24% and a near-zero remnant strain. Using HRTEM, the antiferroelectric nano-domains composited by three variants of in-phase a⁰a⁰c⁺ octahedral tilting coexisted with the remnant ferroelectric nano-domains of anti-phase a^?a^?a^? octahedral tilting are directly identified. Then a continuous tilting model is proposed to interpret the gradually transitional tilting involving nano-domains leading to the small hysteresis and near-zero remnant strain. The findings may pave a way for further optimizing the properties through creating stable antiferroelectric nano-domains in BNT-based ceramics and the analogues.     

Nanoscale origins of small hysteresis and remnant strain in Bi0.5Na0.5TiO3-based lead-free ceramics

BiAlO₃-doped Bi_0.5Na_0.5TiO₃-Bi_0.5K_0.5TiO₃ (BA-doped BNT-BKT) ceramics are greatly concerned due to their sufficient electric-field-induced strain with small hysteresis and remnant strain for high precision positioning devices and other actuators. In this paper, the structural analysis especially the high-resolution transmission electron microscope (HRTEM) is used to reveal the origin of excellent properties obtained in 0.96(0.75BNT-0.25BKT)-0.04BA, which exhibits a large strain of 0.21% at ∼70 kV/cm, a small strain hysteresis of only 24% and a near-zero remnant strain. Using HRTEM, the antiferroelectric nano-domains composited by three variants of in-phase a⁰a⁰c⁺ octahedral tilting coexisted with the remnant ferroelectric nano-domains of anti-phase a⁻a⁻a⁻ octahedral tilting are directly identified. Then a continuous tilting model is proposed to interpret the gradually transitional tilting involving nano-domains leading to the small hysteresis and near-zero remnant strain. The findings may pave a way for further optimizing the properties through creating stable antiferroelectric nano-domains in BNT-based ceramics and the analogues.     

High energy storage density and discharging efficiency in La3+/Nb5+-co-substituted (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

In this work, [(Bi_1-xLa_x)_0.5Na_0.5]_0.94Ba_0.06(Ti_1-5y/4Nb_y)O₃ ceramics have been developed by the dual-substitution of La³⁺ for Bi³⁺ and Nb⁵⁺ for Ti⁴⁺ and prepared by an ordinary sintering technique. All ceramics can be well-sintered at 1200 °C. The addition of La³⁺ and Nb⁵⁺ reduces the grain size and improve the dielectric breakdown strength of the ceramics; moreover, after the introduction of La³⁺ and Nb⁵⁺, the remanent polarization of the ceramics is significantly reduced, while the maximum polarization remains the same large value as that of the ceramic without the doping of La³⁺ and Nb⁵⁺. As a result, high energy storage density and discharge efficiency are achieved at x/y = 0.07/0.02, giving the large storage density of 1.83 J/cm³ and high discharging efficiency of 70%. The present work presents a feasible strategy to develop energy storage materials based on perovskite ferroelectrics by the partial substitutions in the A and B sites.     

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

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

High energy storage density and efficiency in (Bi0.5Na0.5)0.94Ba0.06TiO3-based ceramics with broadened and flattened dielectric peaks

Currently, Bi_0.5Na_0.5TiO₃-based lead-free ferroelectrics have attracted considerable attention as one of the promising candidates for dielectric materials due to their large spontaneous polarization, environmental friendliness and low cost. However, their poor energy density hinder the practical application of the materials. Herein, a novel ceramic of (1-x) (0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃)-x(0.96NaNbO₃-0.04CaSnO₃) (BNBT-xNNCS) has been developed by the solid solution of antiferroelectric NaNbO₃–CaSnO₃ into ferroelectric Bi_0.5Na_0.5TiO₃–BaTiO₃ and the microstructure and electrical properties of the material have been systematically investigated. All the ceramics are lied within the coexistence zone of tetragonal (T) and rhombohedral (R) phases, ensuring to the large polarizations of the materials. Importantly, the introduction of NaNbO₃–CaSnO₃ shifts dielectric peaks at T_s towards room temperature and simultaneously broadens and flattens the dielectric peaks, destroying the ferroelectric long-range order of ferroelectric domains and inducing the generation of polar nanoregions (PNRs) to reduce the remanent polarization. As a result, the prominent energy storage properties with the charge energy storage density (W_tot) of 1.86 J/cm³, recoverable energy density (W_rec) of 1.64 J/cm³ and energy storage efficiency (η) of 88.23% are obtained in the BNBT-xNNCS ceramics with x = 0.20 (BNBT-20NNCS) under a comparatively low electric field strength of 149 kV/cm, accompanying with superior frequency (ΔW_rec ≤ 3%, Δη ≤ 3%, 30–90 Hz) and thermal stability (ΔW_rec ≤ 10%, Δη ≤ 10%, 25–175 °C).     

Giant electro-strain and enhanced energy storage performance of (Y0.5Ta0.5)4+ co-doped 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 lead-free ceramics

0.94(Bi_0.5Na_0.5)(Y_0.5Ta_0.5)_xTi_1-xO₃-0.06BaTiO₃ lead-free piezoelectric ceramics were prepared by a conventional solid-state reaction method to study their excellent electro-strain properties and energy storage characteristics systematically. All ceramics exhibited a dense surface morphology. The introduction of (Y_0.5Ta_0.5)⁴⁺ complex ions destroyed the long-range ferroelectric order, which reduced the T_F-R to the operating temperature, resulting in an easier field-induced transition between relaxor and ferroelectric phase. Therefore, for x = 0.01 component attained unipolar strain of 0.37% under 52 kV/cm, and the corresponding normalized strain d₃₃* was 708 pm/V. Besides, the destruction of the ferroelectric phase also induced a pinched hysteresis loop and the maximum storage density of 1.215 J/cm³ with the efficiency of 68.7% obtained at 98 kV/cm for BNYT30 ceramics. These all demonstrated that the doping of complex ions (Y_0.5Ta_0.5)⁴⁺ made the BNT-BT an outstanding candidate for actuators and energy storage devices.     

Intermediate-temperature conductivity of B-site doped Na0.5Bi0.5TiO3-based lead-free ferroelectric ceramics

Na_0.5Bi_0.5TiO₃ (NBT) based oxide-ion conductor ceramics have great potential applications in intermediate-temperature solid oxide fuel cells (SOFCs) and oxygen sensors. Na_0.5Bi_0.49Ti_1−xMg_xO_3−δ ceramics with x=0, 0.01, 0.02, 0.03, 0.05 and 0.08 were prepared by conventional solid-state reaction. XRD measurement and SEM analysis revealed the formation of pure perovskite structures without secondary phase. MgO doping greatly decreased the sintering temperature and inhibited grain growth. AC impedance spectroscopy measurement was adopted to measure the total conductivity, which was found to increase with MgO doping content ranging from 0 to 3 mol% and subsequently to decrease. High oxygen ionic conductivity σ_t=0.00629 S/cm was achieved for sample doped with 3 mol% MgO at 600 °C in air atmosphere.