High energy-storage properties of [(Bi1/2Na1/2)0.94 Ba0.06] La(1−x) ZrxTiO3 lead-free anti-ferroelectric ceramics

Energy-storage properties of [(Bi_1/2Na_1/2)_0.94Ba_0.06]La_(1−x)Zr_xTiO₃ (BNT-BLZT, x=0, 0.02, 0.04, and 0.06) lead-free anti-ferroelectric ceramics fabricated via the conventional sintering technique were first investigated. Calculation from the X-ray diffraction results reveals that BNT-BLZT ceramic possesses a single perovskite structure phase. In addition, the P–E hysteresis loops measured at room temperature show that the BNT-BLZT (x=0.02) ceramics obtain the maximum P value of 37.5 μC/cm² and the largest energy-storage density W_max is 1.58 J/cm³. The temperature dependence of dielectric permittivity ε_r and dielectric loss tanδ illustrate that the addition of Zr can improve the piezoelectric properties of BT-BLZT ceramics. These properties indicate that BNT-BLZT ceramics might be a promising lead-free anti-ferroelectric material for energy storage application.     

Enhanced ferroelectric properties in (Ba1−xCax)(Ti0.94Sn0.06)O3 lead-free ceramics

Lead-free (Ba_1−xCa_x)(Ti_0.94Sn_0.06)O₃ (BCST) (x = 0.01-0.04) ceramics were prepared using a solid-state reaction technique. The effects of Ca content on the phase structure and electrical properties of the BCST ceramics were investigated. High piezoelectric coefficient of d₃₃ = 440 pC/N, planar electromechanical coupling factor of k_p = 45% and dielectric constant ?_r = 6900 were obtained for the samples at x = 0.03. At room temperature, a polymorphic phase transition (PPT) from orthorhombic phase to tetragonal phase was identified in the composition range of 0.02 < x < 0.04.     

Enhancement of the dielectric,piezoelectric, and ferroelectric properties in BiYbO3-modified (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 lead-free ceramics

Lead-free (1−x)(Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃−xBiYbO₃ [(1−x)BCTZ−xBYO] piezoelectric ceramics in the range of BYO concentrations were prepared by the conventional oxide-mixed method, and the effect of BYO content on their microstructure, crystalline structure, density and electrical properties was investigated. A dense microstructure with large grain was obtained for the ceramics with the addition of BYO. The ceramics with x=0.1% exhibit an optimum electrical behavior of d₃₃~580 pC/N, r~10.9 Ω, k_p~56.4%, and tan δ~1.12% when sintered at a low temperature of ~1350 °C. When the measuring electric field is 40 kV/cm, the well-saturated and square-like P–E loops for the ceramics were observed with P_r~12.2 μC/cm² and E_c~1.83 kV/cm.     

Synthesis and negative thermal expansion property of Y2−xLaxW3O12 (0≤x≤2)

Y_2−xLa_xW₃O₁₂ solid solutions were successfully synthesized by the solid state reaction method. The microstructure, hygroscopicity and thermal expansion property of the resulting samples were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and thermal mechanical analysis (TMA). Results indicate that the structural phase transition of the Y_2−xLa_xW₃O₁₂ changes from orthorhombic to monoclinic with increasing substituted content of lanthanum. The pure phase can form for 0≤x≤0.4 with orthorhombic structure and for 1.5≤x≤2 with monoclinic one. High lanthanum content leads to a low relative density of Y_2−xLa_xW₃O₁₂ ceramic. Thermal expansion coefficients of the Y_2−xLa_xW₃O₁₂ (0≤x≤2) ceramics also vary from −9.59×10⁻⁶ K⁻¹ to 2.06×10⁻⁶ K⁻¹ with increasing substituted content of lanthanum. The obtained Y_0.25La_1.75W₃O₁₂ ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.66×10⁻⁶ K⁻¹ from 103 °C to 700 °C.     

High energy storage performance of [(Bi0.5Na0.5)0.94Ba0.06]0.97La0.03Ti1-x(Al0.5Nb0.5)xO3 ceramics with enhanced dielectric breakdown strength

Novel lead-free [(Bi_0.5Na_0.5)_0.94Ba_0.06]_0.97La_0.03Ti_1-x(Al_0.5Nb_0.5)_xO₃ ceramics (BNBLT-xAN) were prepared by the conventional solid state sintering method. The dielectric, ferroelectric, ac impedance and energy-storage performance were systematically investigated. Temperature dependent permittivity curves showed that relaxation properties of sintered ceramics gradually diminished with the increase of AN. The introduction of AN gave rise to a slimmer polarization hysteresis loop (P-E) and an enhanced dielectric breakdown strength (DBS). Therefore, the optimum energy-storage performance were realized at x?=?0.05 with the energy-storage density (W_rec) of 1.72?J/cm³ and energy-storage efficiency (η) of 85.6% at 105?kV/cm, accompanied with the excellent temperature stability and fatigue performance. The results demonstrated that BNBLT-xAN system was a promising lead-free candidate for energy-storage applications.     

Synthesis and microstructure of (LaSr)MnO3 and (LaSr)FeO3 ceramics by a reaction-sintering process

(La_xSr_1−x)MnO₃ (LSMO) and (La_xSr_1−x)FeO₃ (LSFO) (x = 0.2–0.4) ceramics prepared by a simple and effective reaction-sintering process were investigated. Without any calcination involved, La₂O₃ and SrCO₃ were mixed with MnO₂ (LSMO) or Fe₂O₃ (LSFO) then pressed and sintered directly. LSMO and LSFO ceramics were obtained after 2 and 4 h sintering at 1350–1400 and 1200–1280 °C, respectively. Grain size decreased as La content increased in LSMO and LSFO ceramics.     

Composition and poling condition-induced electrical behavior of (Ba0.85Ca0.15)(Ti1−xZrx)O3 lead-free piezoelectric ceramics

Lead-free (Ba_0.85Ca_0.15)(Ti_1−xZr_x)O₃ (BCTZ) piezoelectric ceramics were fabricated by normal sintering in air atmosphere. BCTZ ceramics with x = 0.10 possess a coexistence of tetragonal and rhombohedral phases at ∼40 °C. The Curie temperature of BCTZ ceramics decreases with increasing the Zr content. Piezoelectric properties of BCTZ ceramics are dependent on the poling conditions (i.e., the poling temperature and the poling electric field), and the underlying physical mechanism is illuminated by the phase angle. The BCTZ (x = 0.10) ceramic, which locates at the existence of two phases and is poled at E ∼ 4.0 kV/mm and T_p ∼ 40 °C, exhibits an optimum electrical behavior at a room temperature of ∼20 °C: d₃₃ ∼ 423 pC/N, k_p ∼ 51.2%, 2P_r ∼ 18.86 μC/cm², 2E_c ∼ 0.47 kV/mm, ?_r ∼ 2892, and tan δ ∼ 1.53%.     

Compositional dependence of phase structure and electrical properties in (K0.50Na0.50)0.97Bi0.01(Nb1−xZrx)O3 lead-free ceramics

(K_0.50Na_0.50)_0.97Bi_0.01(Nb_1-xZr_x)O₃ (KNBNZ) lead-free ceramics were prepared by the conventional solid-state sintering process. Their phase structure is dependent on the Zr content in the investigated range, and the ceramics endure a phase transition from pseudocubic to orthorhombic with increasing Zr content. Improved piezoelectric properties have been observed when the poling temperature is located at ~100 °C because of the coexistence of orthorhombic and tetragonal phases. Their dielectric and piezoelectric properties were enhanced by doping Zr, the ceramic with x=0.02 showing optimal electrical properties, i.e., d₃₃~161 pC/N, k_p~0.41, Q_m~81, T_c~370 °C, and T_o−t~130 °C. These results show that the KNBNZ ceramic is a promising lead-free piezoelectric material.     

Effects of Sb content on electrical properties of lead-free piezoelectric (K0.4425Na0.52Li0.0375) (Nb0.9625−xSbxTa0.0375)O3 ceramics

Lead-free (K_0.4425Na_0.52Li_0.0375) (Nb_0.9625−xSb_xTa_0.0375)O₃ piezoelectric ceramics were prepared by the conventional sintering method. The effects of the Sb content on the phase structure, microstructure, dielectric, piezoelectric, and ferroelectric properties of the (K_0.4425Na_0.52Li_0.0375) (Nb_0.9625−xSb_xTa_0.0375)O₃ ceramics were investigated. The much higher Pauling electronegativity of Sb compared with Nb makes the ceramics more covalent. By increasing x from 0.05 to 0.09, all samples exhibit a single perovskite structure with an orthorhombic phase over the whole compositional range, and the bands in the Raman scattering spectra shifted to lower frequency numbers. The grain growth of the ceramics was improved by substituting Sb⁵⁺ for Nb⁵⁺. Significantly, the (K_0.4425Na_0.52Li_0.0375) (Nb_0.8925Sb_0.07Ta_0.0375)O₃ ceramics show the peak values of the piezoelectric coefficient (d₃₃), electromechanical coupling coefficient (k_p), and dielectric constant (?), which are 304 pC/N, 48% and 1909, respectively, owing to the densest microstructure of typical bimodal grain size distributions. Besides, the underlying mechanism for variations of the electrical properties due to Sb⁵⁺ substitution was explained in this work.     

Microwave dielectric properties of Ba3Ti4−x(Zn1/3Nb2/3)xNb4O21 for low temperature co-fired ceramics

The effects of substitution of (Zn_1/3Nb_2/3) for Ti on the sintering behavior and microwave dielectric properties of Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ (0 ≤ x ≤ 4) ceramics have been investigated. The dielectric constant (?_r) and the temperature coefficient of the resonant frequency (τ_f) of Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ ceramics decreased with increasing x. However, the Q × f values enhanced with the substitution of (Zn_1/3Nb_2/3) for Ti. It was found that a small amount of MnCO₃-CuO (MC) and ZnO-B₂O₃-SiO₂ (ZBS) glass additives to Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ (x = 2) ceramics lowered the sintering temperature from 1250 to 900 °C. And Ba₃Ti_4−x(Zn_1/3Nb_2/3)_xNb₄O₂₁ (x = 2) ceramics with 1 wt% MC and 1 wt% ZBS sintered at 900 °C for 2 h showed excellent dielectric properties: ?_r = 53, Q × f = 14,600 GHz, τ_f = 6 ppm/°C. Moreover, it has a chemical compatibility with silver, which made it as a promising material for low temperature co-fired ceramics technology application.     

Structure,dielectric and piezoelectric properties of Ba0.90Ca0.10Ti1−xSnxO3 lead-free ceramics

Lead-free piezoelectric ceramics Ba_0.90Ca_0.10Ti_1−xSn_xO₃ have been prepared by a conventional ceramic fabrication technique and the effects of Sn⁴⁺ on the structure, dielectric and piezoelectric properties of the ceramics have been investigated. All the ceramics exhibit a pure perovskite structure. After the substitution of Sn⁴⁺, the crystal structure of ceramics is transformed gradually from a tetragonal to an orthorhombic phase, and becomes a pseudo-cubic phase at x≥0.14. The substitution also decreases the Curie temperature greatly from 138 °C at x=0 to 33 °C at x=0.12, and shifts the orthorhombic–tetragonal phase transition to higher temperatures. Coexistence of the orthorhombic and tetragonal phases is formed in the ceramic at x=0.10, leading to significant improvements in the piezoelectric properties: d₃₃=521 pC/N and k_p=45.5%. Our results also reveal that the ceramics sintered at higher temperatures contain larger grains, and thus exhibit more noticeable tetragonal–orthorhombic phase transition and enhanced ferroelectric and piezoelectric properties.     

Dielectric properties of CuO-doped La2.98/3Ba0.01(Mg0.5Sn0.5)O3 ceramics at microwave frequency

The microwave dielectric properties of La_2.98/3Ba_0.01(Mg_0.5Sn_0.5)O₃ ceramics prepared by the conventional solid-state method were investigated for application in mobile communication. A 100 °C reduction of the sintering temperature was obtained by using CuO as a sintering aid. A dielectric constant of 20.0, a quality factor (Q × f) of 50,100 GHz and a temperature coefficient of resonant frequency τ_f of −78.3 ppm/°C were obtained when La_2.98/3Ba_0.01(Mg_0.5Sn_0.5)O₃ ceramics with 0.25 wt.% CuO were sintered at 1500 °C for 4 h.     

Investigation of ternary system Pb(Sn,Ti)O3-Pb(Mg1/3Nb2/3)O3 with morphotropic phase boundary compositions

(1 − x)Pb(Sn_1−yTi_y)O₃-xPb(Mg_1/3Nb_2/3)O₃ (x = 0.1-0.4, y = 0.45-0.65) ternary system was prepared using two-step columbite precursor method. Phase structure of the synthesized ceramics was studied by using X-ray powder diffraction and the morphotropic phase boundary (MPB) curve of the ternary system was confirmed. The isothermal map of Curie temperature (T_C) in the phase diagram was obtained based on the dielectric-temperature measurements. The coercive field E_C and internal bias field E_i were found to increase with increasing PT content, while decrease with increasing PMN content. The optimum properties were achieved in the MPB composition 0.8Pb(Sn_0.45Ti_0.55)O₃-0.2Pb(Mg_1/3Nb_2/3)O₃, with dielectric permittivity ?_r, piezoelectric coefficient d₃₃, planar electromechanical coupling k_p, mechanical quality factor Q_m and T_C of being on the order of 3040, 530pC/N, 55.5%, 320 and 190 °C, respectively, exhibiting potential usage for high power application.     

Phase diagram and properties of Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 polycrystalline ceramics

yPb(In_1/2Nb_1/2)O₃-(1 − x − y)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (yPIN-(1 − x − y)PMN-xPT) polycrystalline ceramics with morphotropic phase boundary (MPB) compositions were synthesized using columbite precursor method. X-ray diffraction results indicated that the MPB of PIN-PMN-PT was located around PT = 0.33-0.36, confirmed by their respective dielectric, piezoelectric and electromechanical properties. The optimum properties were found for the MPB composition 0.36PIN-0.30PMN-0.34PT, with dielectric permittivity ?_r of 2970, piezoelectric coefficient d₃₃ of 450 pC/N, planar electromechanical coupling k_p of 49%, remanent polarization P_r of 31.6 μC/cm² and T_C of 245 °C. According to the results of dielectric and pyroelectric measurements, the Curie temperature T_C and rhombohedral to tetragonal phase transition temperature T_R-T were obtained, and the “flat” MPB for PIN-PMN-PT was achieved, indicating that the strongly curved MPB in PMN-PT system was improved by adding PIN component, offering the possibility to grow single crystals with high electromechanical properties and expanded temperature usage range (limited by T_R-T).     

Y doping and grain size co-effects on the electrical energy storage performance of (Pb0.87Ba0.1La0.02) (Zr0.65Sn0.3Ti0.05)O3 anti-ferroelectric ceramics

(Pb_0.87Ba_0.1La_0.02) (Zr_0.65Sn_0.3Ti_0.05)O₃+x mol% Y (PBLZST-x, x=0–1.25) anti-ferroelectric (AFE) ceramics have been prepared by the solid-state reaction process, and the effect of Y-doping on the microstructure and electrical properties has been investigated. When the Y content increases from 0 mol% to 1.25 mol%, the average grain size of the PBLZST ceramics decreases by more than 3 times (from 4.7 μm to 1.5 μm). The doping and grain size co-effects lead to a significant increase in the AFE-to-FE and FE-to-AFE phase transition electric field (E_F and E_A), and result in a decrease in the width of the double hysteresis loops. As the Y content increases from 0 mol% to 0.75 mol%, the E_F increases from 53 KV/cm to 83 KV/cm and the E_A increases from 35 KV/cm to 72 KV/cm. The large recoverable energy density of 2.75 J/cm³ and the high energy efficiency of 71.5% can be achieved when 0.75 mol% Y is doped. The results indicate that Y-doping is an effective method to modulate the average grain size and improve the energy storage performance of the PBLZST anti-ferroelectric ceramics.     

Effect of La substitution on the structural and electrical properties of BaBi4−xLaxTi4O15

Pure and lanthanum doped barium bismuth titanate BaBi_4−xLa_xTi₄O₁₅ (BBLT, x=0, 0.05, 0.15, 0.30) ceramics were prepared utilizing solid state method. The X-ray diffraction (XRD) data confirmed formation of single-phase Aurivillius compounds while SEM micrographs did not show evident grain size change of doped ceramics. Dielectric properties were investigated in 1.21 kHz to 1 MHz frequency range and in the temperature range of 20 to 727 °C. When Bi³⁺ is substituted with La³⁺, a significant disorder was induced and the material exhibited broadening of the phase transition. Impedance analysis confirmed the presence of two semicircular arcs in doped samples suggesting the existence of grain and grain-boundary conduction. The dc-conductivity and activation energies were evaluated for all compositions.     

Raman scattering, electronic structure and microwave dielectric properties of Ba([Mg1−xZnx]1/3Ta2/3)O3 ceramics

Effects of Zn substitution for Mg on the crystal structure, lattice vibrations and microwave dielectric properties of Ba(Mg_1/3,Ta_2/3)O₃ (BMT) ceramics were investigated. Raman scattering spectra for Ba([Mg_1−xZn_x]_1/3Ta_2/3)O₃ (BMZT) ceramics, with x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0, were measured at room temperature. The Raman result shows a dominance of 1:2 ordered structure at all Zn substitution contents. All Raman modes shift to lower frequencies with increasing Zn substitution. Higher Qf value correlates well with narrower width of the breathing Raman mode A_1g(4) and larger relative intensity of 1:2 long-range-ordered mode E_g(2) in BMZT solid solution. First-principle calculation was performed to investigate the electronic structure of 1:2 ordered BMT and Ba(Zn_1/3,Ta_2/3)O₃ (BZT). Covalent bond between Zn and O in BZT is much stronger than that between Mg and O in BMT due to the Zn 3d orbital. Zn substitution for Mg leads to longer and weaker Ta-O bonds, which may be one reason for the variation of Raman spectroscopy and microwave dielectric properties of BMZT system.     

Effect of Eu doping on structure and electrical properties of lead-free (Bi0.5Na0.5)0.94Ba0.06TiO3 ceramics

Eu-doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT6-xEu, x=0.00–2.00 at%) lead-free piezoelectric ceramics have been synthesized by the solution combustion method. The effect of Eu doping concentration on the phase structure, microstructure and electrical properties of BNBT6 ceramics has been investigated. The XRD analysis confirms that the europium additive incorporates into the BNBT6 lattice and results in a phase transition from the coexistence of rhombohedral and tetragonal phases to a more symmetric pseudocubic phase. The SEM images indicate that the europium additive has little effect on the ceramic microstructure and the average grain size is about 2.0 μm. The electrical properties of BNBT6 ceramics can be improved by appropriate Eu doping. The 0.25 at% Eu doped BNBT6 ceramic presents excellent electrical properties: piezoelectric constant d₃₃=149 pC/N, remnant polarization P_r=40.27 μC/cm², coercive field E_c=2.95 kV/mm, dielectric constant ε_r=1658 and dissipation factor tan δ=0.0557 (10 kHz).     

Electrochemical and structural study of Ce0.8Sm0.2−xLaxO1.9 electrolyte materials for SOFC

Ce_0.8Sm_0.2−xLa_xO_1.9 powders, denoted as La_xSDC (for x=0, 0.01, 0.03, 0.05, 0.07 and 0.1), were synthesized via the mechanical milling reaction method. The La³⁺ doping content has a remarkable influence on structural and electrical properties. The phase identification and morphology were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Lattice parameters were calculated by the Rietveld method. It was observed that the lattice parameter values in Ce_0.8Sm_0.2−xLa_xO_1.9 systems obey Vegard's law. The pellets were then sintered at 1500 °C in air for 7 h. The relative densities of these pellets were over 93.7%.The electrical conductivity was studied using two-probe impedance spectroscopy and results showed that the conductivity of Ce_0.8Sm_0.2−xLa_xO_1.9 first increased and then decreased with La dopant content x. Results also showed that Ce_0.8Sm_0.17La_0.03O_1.9 had the highest electrical conductivity, σ₇₀₀ °C equal to 3.8×10⁻² Scm⁻¹ and an activation energy equal to 0.77 eV. It was therefore concluded that co-doping with the appropriate amount of La can further improve the electrical properties of ceria electrolytes.