Dielectric,ferroelectric and field-induced strain response of lead-free (Fe,Sb)-modified (Bi0.5Na0.5)0.935Ba0.065TiO3 ceramics

Lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.935Ba_0.065Ti_1−x(Fe_0.5Sb_0.5)_xO₃ (BNBT6.5–xFS, x=0.005, 0.010, 0.015, 0.020) were prepared by a conventional solid sintering technique. The effects of B-site doping of (Fe, Sb) on the phase structure, microstructure, dielectric, ferroelectric, and piezoelectric properties of BNBT6.5 ceramics were systematically investigated. Results showed that (Fe, Sb) can completely diffuse in the BNBT6.5 lattice in the all studied components. The addition of (Fe, Sb) destroyed the ferroelectric long-range order, and thus promoted the electric field induced strain response. The maximum electric field-induced strain (S_max=0.37%) with normalized strain (d₃₃*=S_max/E_max=454 pm/V) at an applied electric field of 80 kV/cm was obtained at x=0.015. Temperature dependent measurements of both polarization and strain from room temperature to 120 °C suggested that the origin of the large strain is due to a reversible field-induced ergodic relaxor to ferroelectric phase transformation.     

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.     

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.     

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.     

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.     

Two-step sintering of 0.93Bi0.5Na0.5TiO3-0.07BaTiO3 lead-free piezoelectric material

Two-step sintering (TSS) as an efficient sintering method for obtaining dense microstructure while preventing excess grain growth was used for sintering 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃ composition which is located near the morphotropic phase boundary of this binary system. In order to compare the obtained microstructure and piezoelectric properties, conventional single step sintering (SSS) was also examined. Microstructure evolution during sintering at different temperatures was investigated to find the optimum sintering temperature. Ferroelectric hysteresis loop as well as unipolar strain behavior of optimally sintered ceramics was studied. According to density measurement and microstructure studies of the prepared ceramics, TSS resulted in finer and more dense and uniform microstructure compared to SSS method. As a result remnant polarization of TSSed ceramic was increased by 35% and its coercive field was decreased by 16%. The inverse piezoelectric coefficient of the SSSed and TSSed was obtained 220 and 300 p.m./V, respectively. These values are high enough for practical applications such as actuators. The obtained results clearly showed that TSS is capable of sintering 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃ at temperatures lower than which is required for SSS method. Therefore the composition stoichiometry is maintained after sintering and denser microstructure without abnormal grain growth is obtained which is responsible for improved electrical properties of the piezoceramics.     

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.     

Thermally-stable large strain in Bi(Mn0.5Ti0.5)O3 modified 0.8Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3 ceramics

(1-x)[0.8Bi_0.5Na_0.5TiO₃-0.2Bi_0.5K_0.5TiO₃]-xBi(Mn_0.5Ti_0.5)O₃ (x = 0–0.06, BNKMT100x) lead-free ferroelectric ceramics were prepared via solid state reaction method. Bi(Mn_0.5Ti_0.5)O₃ induces a structure transition from rhombohedral-tetragonal morphotropic phases to pseudo-cubic phase. Moreover, the wide range of compositions within x = 0.03–0.055 exhibit large strain of 0.31%–0.41% and electrostrictive coefficient of 0.027–0.041 m⁴/C². Especially, at x = 0.04, the large strain and electrostrictive coefficient are nearly temperature-independent in the range of 25–100 °C. The impedance analysis shows the large strain and electrostrictive coefficient originate from polar nanoregions response due to the addition of Bi(Mn_0.5Ti_0.5)O₃.     

BaTiO3 nanowires-induced phase transition and thermally stable strain in (Bi0.5Na0.5)TiO3 piezoelectric ceramics

Environment-friendly lead-free piezoceramics with high strain response and extremely excellent stability in a wide operating temperature range are critically important in practical actuator applications. Here, we develop a new strategy to tune the electrostrictive strain behavior in Bi_0.5Na_0.5TiO₃ (BNT)-based ceramics via using high aspect ratio BaTiO₃ nanowires (BT NWs) as a modifier. The addition of BT NWs generates a crossover from a typical ferroelectric (BT conventional spherical particles) to a complete ergodic relaxor (ER) phase at ambient temperature, accompanied by a large electrostrictive strain of ∼0.17% with d₃₃*(S_max/E_max) = 284 pm/V. Such a high electrostrictive strain is extremely thermally stable with only <7% fluctuation from 27 °C to 120 °C. In addition, the BT NWs-modified ceramics also exhibit acceptable fatigue endurance (<30% up to 10⁵ cycles) and frequency dependence (<20% at 10Hz–100Hz). These achieved exceptional performances can be ascribed to the BT NWs-driven complete ER phase at room temperature. The findings of this study can inspire enhanced interest in nanowires as a viable modifier to BNT-based materials due to promising potential for practical actuator applications in a wide temperature range.     

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.     

Dielectric,ferroelectric and field-induced strain behavior of K0.5Na0.5NbO3-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

Lead-free piezoelectric (1 ? x)Bi_0.5(Na_0.78K_0.22)_0.5TiO₃–xK_0.5Na_0.5NbO₃ (BNKT–xKNN, x = 0–0.10) ceramics were synthesized using a conventional, solid-state reaction method. The effect of KNN addition on BNKT ceramics was investigated through X-ray diffraction (XRD), dielectric, ferroelectric and electric field-induced strain characterizations. XRD revealed a pure perovskite phase with tetragonal symmetry in the studied composition range. As the KNN content increased, the depolarization temperature (T_d) as well as maximum dielectric constant (?_m) decreased. The addition of KNN destabilized the ferroelectric order of BNKT ceramics exhibiting a pinched-type hysteresis loop with low remnant polarization (11 μC/cm²) and small piezoelectric constant (27 pC/N) at 3 mol% KNN. As a result, at x = 0.03 a significant enhancement of 0.22% was observed in the electric field-induced strain, which corresponds to a normalized strain (S_max/E_max) of ～434 pm/V. This enhancement is attributed to the coexistence of ferroelectric and non-polar phases at room temperature.     

Electric field-induced irreversible relaxor to ferroelectric phase transformations in Na0.5Bi0.5TiO3-NaNbO3 ceramics

(1-x)Na_0.5Bi_0.5TiO₃-xNaNbO₃ (x = 0.02, 0.04, 0.06, and 0.08) ceramics were fabricated by solid-state reaction. High-resolution synchrotron x-ray powder diffraction (SXPD) data, coupled with macroscopic electromechanical measurements, reveal the occurrence of an electric field-induced irreversible crystallographic transformation for x = 0.02 and 0.04, from a pseudo-cubic non-ergodic relaxor to a rhombohedral or coexisting rhombohedral-tetragonal long range-ordered ferroelectric phase, respectively. The highest unipolar electrostrain, corresponding to an effective longitudinal piezoelectric strain coefficient of approximately 340 pm V⁻¹, was obtained for x = 0.04; this effect is attributed to enhanced domain switching as a result of the co-existing rhombohedral and tetragonal phases for this composition, which is critical for piezoelectric actuator applications.     

Electrical properties and relaxor phase evolution of Nb-Modified Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3-SrTiO3 lead-free ceramics

In this work, the crystalline phase, domain structure, and electrical properties of [Bi_0.5(Na_0.84K_0.16)_0.5]_0.96Sr_0.04Ti_1-xNb_xO₃ (x = 0.010–0.030) ceramics are investigated. Increasing the Nb content induces the phase transition from coexistent rhombohedral and tetragonal phases to a single pseudo-cubic phase, and the lamellar ferroelectric domains evolve into polar nanoregions. Decreased ferroelectric-to-relaxor transition temperature and enhanced frequency dispersion are found in the temperature-dependent dielectric constant and loss, implying a transition from the non-ergodic to ergodic relaxor state. The Nb substitution significantly degrades the long-range ferroelectric order with sharply decreased piezoelectric coefficients from ? 140 to ? 1 pC/N. However, a large strain of 0.32% at 5 kV/mm (normalized strain of 640 pm/V) is obtained around the critical composition of x = 0.0225. The composition of x = 0.030 shows good temperature insensitivity of the strain response, characterized by 308 pm/V with less than 15% reduction from 25 °C to 125 °C.     

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.     

Giant electric field-induced strain and structure evolution of NaTaO3-modified 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 Pb-free ceramics

To acquire giant electric field-induced strain in non-Pb materials is attracting a great deal of attention in the past decade. In the current investigation, the crystal and domain structures as well as the electrical performances of (1-x) (0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃)-xNaTaO₃ (BNBT-xNT) specimens were systematically studied to achieve enhanced strain. The introduction of NT makes the phase structure transit from rhombohedral-tetragonal to pseudo-cubic structure. The original domain structure of BNBT is destroyed, and the disorder degree of the local structure increases. Simultaneously, the remnant polarization, coercive field, and piezoelectric coefficients were significantly decreased. The transition from ferroelectric to ergodic relaxation can be effectively modified, thus lowering the transition zone to room temperature. Finally, the BNBT-3NT ceramics achieve marked strain coefficients at room temperature, with a maximum strain of 0.394% under 65 kV/cm and a d₃₃* of 606 pm/V.     

Improved electric-field-induced strain and strong photoluminescence properties in novel Er3+-modified 0.93Bi0.5Na0.5TiO3-0.07BaTiO3 multifunctional ceramics

Recently, the progress of electronic devices toward miniaturization has strongly promoted development of multifunctional materials possessing multiple desirable properties. In this study, we develop and fabricate 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃-xEr multifunctional ceramics which show simultaneously considerable electric-field-induced strain and bright green light emission properties. With the introduction of Er³⁺, the ceramics gradually transform from non-ergodic relaxor phase to ergodic relaxor phase which could reversibly transform to ferroelectric phase under the electric field. As a result, with improving Er³⁺ content, the shape of the polarization-electric field loops of the ceramics become pinched, and it is obvious that the negative strain disappears while the positive strain gradually increases and reaches a maximum value 0.46% at x = 1.2 mol%. Besides, After the ceramics are poled, the light emission peak are greatly enhanced attributed to the decreased crystal symmetry and increased domain size, and is the strongest at x = 1.2 mol%. These results indicate that 0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃-xEr ceramics are good candidates for developing multifunctional optoelectronic devices.     

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.     

Large electrostrain and high energy-storage of (1-x)[0.94(Bi0.5Na0.5) TiO3-0.06BaTiO3]-xBa(Sn0.70Nb0.24)O3 lead-free ceramics

(1-x)[0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃]-xBa(Sn_0.70Nb_0.24)O₃ (abbreviated as BNTBT-100xBSN) lead-free ceramics were fabricated with a relative density greater than 96 %, and the structure as well as performance were tested. BNTBT-100xBSN ceramics are pseudo-cubic perovskite structure, with dense surface morphology. Doping BSN can effectively reduce the dielectric loss of ceramics and increase the relaxation properties to a certain extent. The randomly distributed ferroelectric phase was replaced by polar nano regions, thereby improving the electro-strain and energy storage performance of the system. The largest electro-strain and the corresponding normalized strain (d₃₃*) reach ~ 0.43 % and 633 pm/V respectively in the BNTBT-1BSN ceramic. The largest effective energy storage density reaching ~ 1.28 J/cm³ was tested in BNTBT-2BSN. BNTBT-100xBSN ceramics provide a feasible idea for the systematic research of lead-free ferroelectrics and improvements in electro-strain and energy storage applications.     

Tuning the electrocaloric effect in 0.94Bi0.5Na0.5TiO3-0.06BaTiO3 ceramics by relaxor phase blending

The pseudo-first-order phase transition in 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ ceramics leads to a sharp increase in temperature change (ΔT) in the vicinity of the ferroelectric-to-relaxor transition temperature T_FR (~100 °C) [Appl. Phys. Lett. 110 (2017) 182904]. In this study, we add the 0.78Bi_0.5Na_0.5TiO₃-0.06BaTiO₃-0.16(Sr_0.7Bi_0.2)TiO₃ relaxor phase to the 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ ferroelectric matrix to tune its electrocaloric effect. The results show that the addition of the relaxor phase plays a vital role in phase and local-structure evolution. A transition occurs between the ferroelectric and ergodic relaxor phases when the mass fraction of the latter increases to 30% (x = 0.3), as verified by X-ray diffraction analysis, Raman spectroscopy, and polarization-electric field (P-E) hysteresis loops. Furthermore, addition of the relaxor phase reduces the T_FR from 76 °C at x = 0.1–55 °C at x = 0.2; however, this transition disappears at x = 0.3 and 0.4 composite. In-situ piezo-force microscopy (PFM) images illustrate that domains can be written into x = 0.1 and 0.2 ceramics with a valley in the piezoresponse curves. Increasing the temperature agitates the domain arrangement and decreases the contrast for PFM images; this indicates a gradual phase transition in the composite. The temperature corresponding to maximum ΔT exhibits a downward shift (0.58 K at 80 °C for x = 0.1 and 0.5 K at 65 °C for x = 0.2), while the temperature-ΔT curves are flat when x = 0.3 and 0.4. Moreover, the maximum ΔT shows a decrease with an increase in the relaxor phase content; this is believed to be related to a decrease in the latent heat due to a pseudo-first-order to second-order transition. Thus, we suggest that the incorporation of a relaxor phase into ferroelectric matrices is an effective technique to tune their electrocaloric effect and improve the thermal stability of ceramic composites.     

Microstructure and suppressed thermal depolarisation behaviours of lead-free Na0.5Bi0.5TiO3:ZnO ferroelectric composite ceramics

ABSTRACT

A 0–3 type 0.8Na_0.5Bi_0.5TiO₃(BNT):0.2ZnO lead-free ferroelectric composite ceramic structure was prepared by a solid-state oxide route. The X-ray diffraction analysis and scanning electron microscopy observation indicate that ZnO grains were scattered in the matrix consisting of BNT grains to form a (0–3) type composite structure, and a third phase Zn₂TiO₄ was formed due to the reaction ability of nano-sized ZnO with NBT compositions. The temperature-dependent electrical responses show that the dielectric anomaly at around 200°C inherited from NBT itself was suppressed as ZnO is composited, and the P_r of the specimen sintered at 1000°C keeps almost unchanged as the poling temperature is 175°C, while its retained piezoelectric strain d₃₃ value maintains 77% of the initial as exposed to 125°C annealing. These results suggest that the thermal depolarisation of BNT is suppressed due to the introduction of ZnO, even though the third phase Zn₂TiO₄ exists.