Sodium‐potassium niobate nanorods with various crystal structures and their application to nanogenerator

(Na_1?xK_x)NbO₃ (NKN) nanorods with an orthorhombic (OR) structure, a rhombohedral (RH) structure, or a polymorphic phase (PP) structure, which contains both OR and RH structures, are prepared. The presence of RH and PP NKN nanorods is explained by the existence of OH^? defects at the O^2? sites of the NKN nanorods. The PP NKN nanorods grown on a Nb⁵⁺‐doped SrTiO₃ substrate show the largest piezoelectric strain constant of 175 pm/V because they have more directions for dipole rotation than OR and RH NKN nanorods. Piezoelectric nanogenerators (NGs) are synthesized using composites consisting of NKN nanorods with various structures and polydimethylsiloxane. The largest open‐circuit output voltage is 35 V, and the short‐circuit current is 5.0 μA, which are obtained using the NG containing 0.7 g of PP NKN nanorods. Moreover, this NG shows a maximum output power of 16.5 μW for an external load of 10.0 MΩ.     

Synthesis of [10Ῑ]‐Oriented (Na1−xKx)NbO3 Platelets by Using Hydrothermally Produced (K8−8xNa8x)Nb6O19·nH2O Precursor

Micrometer size [10] (N_1?xK_x)NbO₃ (NKN) platelets were synthesized by annealing (K_8?8xNa_8x)Nb₆O₁₉·nH₂O (KNNH) precursors at 500°C. The plate‐like KNNH precursors were produced from (1?y)NaOH‐yKOH + Nb₂O₅ specimens using the hydrothermal process at 160°C. The size of the NKN platelets was similar to that of the KNNH precursor, but the surfaces of the NKN platelets were rough while the KNNH precursor had a smooth surface. The formation of a rough surface is related to the vigorous evaporation of the H₂O from the KNNH platelets during the annealing process at high temperatures. NKN platelets with smooth surfaces could be synthesized using KNNH platelets, which were heated to 150°C to evaporate H₂O before annealing at 500°C. These NKN platelets can be used for the fabrication of textured NKN ceramics.     

Structural and thermoelectric properties of hydrothermal-processed Ag-doped Fe2O3

Fe_2-xAg_xO₃ (0?≤?x?≤?0.04) nanopowders with various Ag contents were synthesized at different hydrothermal reaction temperatures (150?°C and 180?°C). Their structural properties were fully investigated through an X-ray diffraction, a Fourier transform infrared spectroscopy, and an X-ray photoelectron spectroscopy. The hydrothermal reaction temperature, time, and Ag content remarkably affected the morphological characteristics and crystal structure of the synthesized powders. The Fe_2-xAg_xO₃ (0?≤?x?≤?0.04) powders synthesized at 150?°C for 6?h and the Fe_2-xAg_xO₃ (0.02?≤?x?≤?0.04) powders synthesized at 180?°C for 12?h formed the orthorhombic α-FeOOH phase with a rod-like morphology, whereas the Fe_2-xAg_xO₃ (0?≤?x?≤?0.01) powders synthesized at 180?°C for 12?h formed the rhombohedral α-Fe₂O₃ phase with a spherical-like morphology. The Fe_1.98Ag_0.02O₃ fabricated by utilizing Fe_1.98Ag_0.02O₃ powders synthesized at 180?°C showed the largest power factor (0.64?×10^?5 Wm^?1 K^?2) and dimensionless figure-of-merit (0.0036) at 800?°C.     

Phase structure and electrical properties of lead free Na0·5Bi0·5TiO3–CaTiO3 ceramics

Abstract

Abstract

(1?x)Na_0·5Bi_0·5TiO_3?xCaTiO₃ ceramics with x?=?0–0·2 were prepared by solid state sintering method. Structural and morphology studies carried out by X-ray diffraction and scanning electron microscopy indicate the change in crystal structure from rhombohedral to orthorhombic symmetry (R3C to Pnma). The morphotropic phase boundary of this system was found to lie around x?=?0·08–0·14, where the orthorhombic and rhombohedral symmetries coexist. The orthorhombic phase is stabilised for x>0·14, indicating that the rhombohedral phase of Na_0·5Bi_0·5TiO₃ is susceptible to orthorhombic distortion brought about by Ca substitution. Calcium substitution in Na_0·5Bi_0·5TiO₃ caused an obvious decrease in peak temperature and a decrease in relative permittivity. The compositional variation of the fundamental dielectric behaviour is discussed in relation to the crystal chemistry of the system. The highest piezoelectric constant d₃₃ of 85 pC N^?1 is achieved for x?=?0·1, with the coercive field of 18 kV cm^?1 and the dielectric maximum temperature of 148°C.     

Dielectric and Raman Spectroscopic Studies of Na0.5Bi0.5TiO3–BaSnO3 Ferroelectric System

A series of lead‐free perovskite solid solutions of (1 ? x) Na_0.5Bi_0.5TiO₃(NBT)—x BaSnO₃(BSN), for 0.0 ≤ x ≤ 0.15 have been synthesized using a high‐temperature solid‐state reaction route. The phase transition behaviors are studied using dielectric and Raman spectroscopic techniques. The ferroelectric to relaxor phase transition temperature (T_FR) and the temperature corresponding to maximum dielectric permittivity (T_m) are estimated from the temperature‐dependent dielectric data. Dielectric studies show diffuse phase transition around ~335°C in pure NBT and this transition temperature decreases with increase in x. The disappearance of x‐dependence of A₁ mode frequency at ~134 cm^?1 for x ≥ 0.1 is consistent with rhombohedral‐orthorhombic transition. In situ temperature dependence Raman spectroscopic studies show disappearance and discontinuous changes in the phonon mode frequencies across rhombohedral (x < 0.1)/orthorhombic (x ≥ 0.1) to tetragonal transition.     

Effects of cerium on structures and electrical properties of (Nb,Ta) modified Bi4Ti3O12 piezoelectric ceramics

Bi₄Ti₃O₁₂ high-temperature piezoelectric ceramics composed of 0.03 mol (Nb, Ta)⁵⁺ substituting B site and x mol CeO₂ (x = 0–0.05, abbreviated as BCTNT100x) substituting A site were synthesized by the conventional solid-state reaction method. The effects of Ce additive on the structures and electrical properties of resulting Bi₄Ti₃O₁₂-based ceramics were systematically investigated. In-situ temperature-dependent X-ray diffraction (XRD) confirmed that the phase structure of BCTNT100x ceramics change from orthorhombic structure to tetragonal structure as temperature increased. The ceramics at Ce content x = 0.03 illustrated optimal performances with superior piezoelectric constant (d₃₃ = 36.5 pC/N), high Curie temperature (T_C = 649 °C), and large remanent polarization (2P_r = 21.6 μC/cm²). BCTNT3 ceramics also possessed high d₃₃ of 32.5 pC/N at an annealing temperature of 600°C, with electrical resistivity preserved at 10⁶ Ω cm at 500 °C. These results demonstrate that BCTNT100x ceramics can be used as high-temperature piezoelectric devices.     

(Na,K)NbO3–CaCu3Ti4O12 perovskite composites for supercapacitor based piezoelectric devices

The supercapacitor based piezoelectric material composite (Na,K)NbO₃–CaCu₃Ti₄O₁₂ (NKN–CCTO) is investigated for possible application in piezoelectric devices. (1−x)NKN–xCCTO (0.015≤x≤0.06) with different sintering conditions is researched for supercapacitor based piezoelectric applications. The 0.94NKN–0.06CCTO composite sintered at 975 °C shows the highest dielectric permittivity of 796. Clear SEM images of (1−x)NKN–xCCTO reveal that these compositions have high density well-crystallized structures. The composition and sintering temperature dependence of dielectric permittivities and piezoelectric coefficients, plotted in three dimensions, show that the 0.985NKN–0.015CCTO composite sintered at 1025 °C has a moderate dielectric permittivity of 405 and a piezoelectric constant of 98 pC/N.     

One‐Step Surfactant‐Free Hydrothermal Synthesis of Platelike Sodium Niobate Template Powders

A one‐step surfactant‐free hydrothermal route is developed to prepare platelike NaNbO₃ template powders. At optimal KOH concentration, pure platelike NaNbO₃ with rhombohedral structure (width and thickness of 20 and 2 μm, respectively) is obtained at 200°C for 16 h. After calcination at 600°C for 4 h, the structure of the hydrothermally synthesized NaNbO₃ changes from rhombohedral to orthorhombic, whereas the initial platelike morphology is maintained. Such characteristics in terms of phase structure, elemental composition, and morphology render our hydrothermally synthesized NaNbO₃ suitable for textured ceramic fabrications.     

Piezoelectric properties of (1-x)BZT-xBCT system for energy harvesting applications

In this study, we investigated (1-x)Ba(Zr_0.2Ti_0.8)O₃–x(Ba_0.7Ca_0.3)TiO₃ lead-free piezoelectric ceramics for energy harvester applications. The (1-x)BZT-xBCT ceramic is a promising lead-free piezoelectric material in the field of piezoelectric energy harvesting. Piezoelectric and energy properties of (1-x)BZT-xBCT ceramics were analyzed to confirm the possibility of using them as energy-harvesting materials. Especially, the vicinity of the phase convergence region was investigated to improve their piezoelectric properties. In the phase convergence region, cubic, rhombohedral, orthorhombic, and tetragonal regions co-exist within the narrow region. Near the phase transition region between the orthorhombic and tetragonal phase, the highest piezoelectric property d₃₃?=?464 pC/N and the highest energy density of 158.5 μJ/cm³ were observed. This output energy density of 158.5 μJ/cm³ is the recorded highest value among lead-free ceramics. We found that the optimal sintering temperature was 1475?°C and the optimal composition was BZT-0.5BCT.     

Crystal growth and ferroelectric property of Na0.5K0.5NbO3 and Mn-doped Na0.5K0.5NbO3 crystals grown by floating zone method

Na_0.5K_0.5NbO₃ (NKN) and Mn-doped NKN crystals, which are one of the promising candidates of lead-free piezoelectric materials, were grown by using a floating zone (FZ) method. The resulting crystal growth was compared with crystal growth that resulted from using a flux method in a previous study. In the crystal grown by FZ method under where the growth rate was controlled to 3 mm/h, thin layers formed parallel and perpendicular directions to the growth direction. In the crystal grown by FZ method, the crystal structure could not be classified as having the orthorhombic lattice of Amm2, which was observed in the crystal grown using a flux method. It was found that doped Mn was substituted in the perovskite-type lattice of NKN. Pure NKN crystals showed 90° domains that had a zig-zag shape, whereas Mn-doped NKN crystals were aligned to the domain layers in straight lines. It was confirmed that Mn-doped NKN crystal showed a square P–E hysteresis loop.     

Effects of Octahedral Tilting on the Piezoelectric Properties of Strontium/Barium/Niobium-Doped Soft Lead Zirconate Titanate Ceramics

(Pb_1−x−ySr_xBa_y)(Zr_0.976−zTi_zNb_0.024)O₃ solid solutions have been investigated to understand the relationship between structural changes caused by isovalent strontium and barium substitution on the A-site and dielectric and piezoelectric properties. As strontium and barium were substituted for lead, the zirconium:titanium (Zr:Ti) ratio was modified so that all compositions had an optimized piezoelectric coefficient (d₃₃). The value of d₃₃ was at a maximum in the tetragonal phase near, but not at, the morphotropic-phase boundary (MPB). The real MPB was taken as the Zr:Ti ratio at which X-ray diffraction patterns appeared either pseudocubic or a mixture of rhombohedral and tetragonal. As strontium content increased, optimized d₃₃ also increased from 410 pC/N (x= 0) to 640 pC/N (x= 0.12), commensurate with a decrease in the paraelectric-to-ferroelectric phase transition temperature (T_C) from 350°C (x= 0) to 175°C (x= 0.12). However, for ceramics where x > 0.12, optimized d₃₃ decreased even though the phase-transition temperature was ∼150°C. Low strontium concentration ceramics (x= 0–0.08) contained 80 nm ferrroelectric domains typical of PZT, but high strontium concentration ceramics (x= 0.12–0.16) contained fine-scale domains (20 nm) in some regions of the microstructure. In addition, [110] pseudocubic electron diffraction patterns revealed superlattice reflections at 1/2{hkl} positions associated with rotations of the octahedra in antiphase. Co-doping ceramics with strontium (x= 0.06) and barium (y= 0.06) resulted in the disappearance of the 1/2{hkl} reflections. Optimized d₃₃ (∼520 pC/N, T_C∼ 205°C) for this composition was similar to that of ceramics where x= 0.08, y= 0, which had a T_C of ∼250°C.     

Electrical Properties of a 0.95(Na0.5K0.5)NbO3–0.05CaTiO3 Thin Film Grown on a Pt/Ti/SiO2/Si Substrate

An amorphous phase was formed in a 0.95(Na_0.5K_0.5)NbO₃–0.05CaTiO₃ (NKN‐CT) film grown at 300°C, and a low‐temperature transient Ca₂Nb₂O₇ phase was formed in the film grown at 500°C. In films grown at high temperatures (≥600°C), secondary phases such as K_5.75Nb_10.85O₃₀ and K₄Ti₁₀Nb₂O₂₇ were developed without the formation of a NKN‐CT phase, probably because of Na₂O evaporation. The same secondary phases were formed in the film grown at 300°C and subsequently annealed at 850°C under an air atmosphere. However, a homogeneous NKN‐CT phase was formed in films grown at 300°C and subsequently annealed at 830°C–880°C under the K₂O and Na₂O atmospheres. Moreover, the film annealed at 830°C in particular exhibited good electric and piezoelectric properties, including a high dielectric constant of 747 with a low dissipation factor of 0.93% at 100 kHz, low leakage current density of 2.0 × 10^?7 A/cm² at 0.1 MV/cm, and high P_r and d₃₃ values of 15.4 μC/cm² and 124 pm/V at 100 kV/cm, respectively.     

Synthesis,characterization, and magneto‐electric properties of (1−x)BCZT‐xCFO ceramic particulate composites

Synthesis of a new magnetoelectric [(1?x)(Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃‐xCoFe₂O₄] (weight fraction x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 1) ceramic particulate composites with its structural characterization and magneto‐electric properties have been reported here in this study. Lead free piezoelectric (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ (BCZT) and ferrimagnetic CoFe₂O₄ (CFO) were synthesized using sol‐gel and combustion methods respectively. (1?x)BCZT‐xCFO magnetoelectric composites were then synthesized by mixing of the calcined individual ferroic phases with required weight fractions. Powder X‐ray diffraction studies indicate the coexistence of BCZT and CFO phases in the composites sintered at 1300°C. 0.5BCZT‐0.5CFO composite showed high strain sensitivity (dλ/dH) of 52×10^?9 Oe^?1, which is comparable to that of pure CFO (50×10^?9 Oe^?1). A high piezoelectric voltage constant (g₃₃) of 8×10^?3 V m/N was measured for 0.8BCZT‐0.2CFO sample. All the composites showed magnetoelectric effect and a high magnetoelectric coupling coefficient (α_ME) of 6.85 mV/cm Oe was measured for 0.5BCZT‐0.5CFO composite at 1 kHz and a large ME coefficient of 115 mV/cm Oe at its resonance frequency. The effect of microstructure on the magnetoelectric properties of [(1?x)BCZT‐(x)CFO] composites has been studied and reported here as a function of its piezoelectric (BCZT)/ferrite (CoFe₂O₄) content.     

High‐Performance (Na0.5K0.5)NbO3 Thin Film Piezoelectric Energy Harvester

The pseudocubic structure of a (Na_0.5K_0.5)NbO₃ (NKN) film grown on a Pt/Ti/SiO₂/Si substrate changed to an orthorhombic structure when the film was transferred onto a polyimide substrate. Piezoelectric constant for the transferred NKN film increased considerably from 74 ± 11 to 120 ± 18 pm/V because the crystal structure of the film had changed from pseudocubic to orthorhombic. A gold interdigitated electrode was deposited onto the transferred NKN film to synthesize a NKN piezoelectric energy harvester. The NKN piezoelectric energy harvester was poled before bending under a 100 kV/cm DC electric field across the electrodes. When a strain of 0.85% and a strain rate of 4.05%/s were applied to the NKN piezoelectric energy harvester, it produced a maximum output voltage of 1.9 V and a current of 38 nA, corresponding to a power density of 2.89 μW/cm³.     

Morphological evolution of PbTiO3 microstructures synthesized by topochemical microcrystal conversion

PbTiO₃ (PT) microstructures were fabricated by topochemical microcrystal conversion (TMC) and their morphological evolution was investigated with variation of synthesis temperature and relative molar ratio of reactants. Using molten salt synthesis, Aurivillius phase of PbBi₄Ti₄O₁₅ (PBiT) synthesized at 1050°C was prepared as precursor. Large plate-like PT microstructures with lengths of hundreds of micrometer were optimally obtained when the relative ratio (x) of (PbCO₃)₂·Pb(OH)₂ to PBiT in reactants was 6. In addition, relatively homogeneous PT platelets were achieved at the annealing temperature of 1050°C by TMC; these materials are probably suitable for use in templated grain growth. However, a Pb-deficient secondary phase of PbTi₃O₇ formed in cases of low x values of less than 4 and low annealing temperatures of less than 1050°C. The porous PT pellets, orthogonally assembled by numerous PT platelets, were achieved by increasing temperature to 1100°C. Further increase in temperature to 1150°C could lead to partial formation of denser PT blocks.     

Dielectric,ferroelectric, and energy storage properties in dysprosium doped sodium bismuth titanate ceramics

In this work, Na_0.5(Bi_1-xDy_x)_0.5TiO₃ (0?≤?x?≤?15%) ceramics were prepared via solid state reaction method and were characterized. A stable and pure perovskite phase was revealed by X-ray diffraction analysis for all compositions and a symmetry change from rhombohedral to orthorhombic phase was detected beyond 10% of Dy substitution. The incorporation of Dy³⁺ into Sodium Bismuth Titanate (Na_0.5Bi_0.5TiO₃) matrix allows a substantial decrease of the coercive field, an increase in the resistivity, and leads to a high stability of the dielectric permittivity (??/?_(150?°C) ≤?±?15%) over a wide temperature range. Furthermore, this system was found to exhibit improved energy storage properties at high temperatures with a maximum energy density of 1.2?J/cm³ obtained for 2%Dy composition at 200?°C. The obtained results are very promising for energy storage capacitors operating at high temperatures.     

Orthorhombic‐pseudocubic phase transition and piezoelectric properties of (Na0.5K0.5)(Nb1−xSbx)‐SrZrO3 ceramics

0.96(Na_0.5K_0.5)(Nb_1?xSb_x)‐0.04SrZrO₃ ceramics with 0.0≤x≤0.06 were well sintered at 1060°C for 6 hours without a secondary phase. Orthorhombic‐tetragonal transition temperature (T_O‐T) and Curie temperature (T_C) decreased with the addition of Sb₂O₅. The decrease in T_C was considerable compared to that in T_O‐T, and thus the tetragonal phase zone disappeared when x exceeded 0.03. Therefore, a broad peak for orthorhombic‐pseudocubic transition as opposed to that for orthorhombic‐tetragonal transition appeared at 115°C‐78.2°C for specimens with 0.04≤x≤0.06. An orthorhombic structure was observed for specimens with x≤0.03. However, the polymorphic phase boundary structure containing orthorhombic and pseudocubic structures was formed for the specimens 0.04≤x≤0.06. Furthermore, a specimen with x=0.055 exhibited a large piezoelectric strain constant of 325 pC/N, indicating that the coexistence of orthorhombic and pseudocubic structures could improve the piezoelectric properties of (Na_0.5K_0.5)NbO₃‐based lead‐free piezoelectric ceramics.     

Enhanced insulation and piezoelectric properties of 0.57(Bi0.8La0.2)FeO3-0.43PbTiO3 solid solutions with Fe addition

0.57(Bi_0.8La_0.2)FeO₃-0.43PbTiO₃-x mol%Fe₂O₃ ceramics (BLF-PT-xFe, x = 0, 0.025, 0.05, 0.125, and 0.25) were prepared by the conventional solid-state reaction method. X-ray diffraction (XRD) reveals that all samples display the perovskite structure with a coexistence of tetragonal (T) phase and rhombohedral (R) phase, while the incorporation of Fe promotes the phase transition from T to R. Scanning electron microscopy (SEM) images show that all samples are well crystallized and their grain size increases noticeably with the increase of Fe content. X-ray photoelectron spectroscopy (XPS) results indicate that Fe doping significantly inhibits the formation of oxygen vacancies, thereby improving insulation of BLF-PT-xFe ceramics. Interestingly, the Curie temperature of BLF-PT-xFe is around 330°C, little changing with the variation of Fe content. However, the depolarization temperatures of BLF-PT ceramics with Fe are 50°C higher than that of the sample without Fe doping. The hopping of second ionized oxygen vacancies are the major carriers in the temperature range of 200°C–500°C. The optimal component of BLF-PT-xFe ceramics appear at x = 0.05, where the dielectric loss tanδ, AC resistivity (200°C), and piezoelectric coefficient d₃₃ could be 0.015, 7 × 10⁶ Ω cm, and 245 pC/N, respectively. All these results indicate that the Fe addition is an effective method to enhance dielectric and piezoelectric properties.     

Piezoelectric properties of (Na0.5K0.5)(Nb1‐xSbx)O3‐SrTiO3 ceramics with tetragonal‐pseudocubic PPB structure

CuO‐added 0.96(Na_0.5K_0.5)(Nb_1‐xSb_x)O₃‐0.04SrTiO₃ ceramics sintered at the low temperature of 960°C for 10 hours showed dense microstructures and high relative densities. The specimens with 0.0 ≤  x ≤ 0.04 had orthorhombic‐tetragonal polymorphic phase boundary (PPB) structure. Tetragonal‐pseudocubic PPB structure was observed in specimens with 0.05 ≤  x ≤ 0.07, while the specimen with x = 0.08 has a pseudocubic structure. The structural variation in the specimens is explained by the decreases in the orthorhombic‐tetragonal transition temperature and Curie temperature with the addition of Sb⁵⁺ ions. The specimens with 0.05 ≤  x ≤ 0.07, which have tetragonal‐pseudocubic PPB structure, had large electric field‐induced strains of 0.14%‐0.016%. Moreover, these specimens also showed increased d₃₃ values between 280 pC/N and 358 pC/N. In particular, the specimen with x = 0.055 showed particularly enhanced piezoelectric properties: d₃₃ of 358 pC/N, k_p of 0.45, and the electric field‐induced strain of 0.16% at 4.5 kV/mm.