Enhancing energy harvesting potential of (K,Na,Li)NbO3‐epoxy composites via Li substitution

In this study, the influence of Li substitution on the piezoelectric performance of lead‐free K_0.5Na_0.5NbO₃ (KNN)‐epoxy composites is explored. KNN piezoceramic particles modified with 0‐12 mol% of Li are prepared via a double calcination technique, resulting in a perovskite particulate which transitions from an orthorhombic to tetragonal crystal structure between 6 and 9 mol% of Li, and contains a minor nonperovskite second phase from 6 mol%. A cuboid particle morphology is evident in all cases, though tetragonal KNN‐based particles have formed with serrated edges and fractures. The particles are dispersed at 10 vol% in an epoxy matrix to develop both random and dielectrophoretically structured (K,Na,Li)NbO₃‐epoxy composites. The dielectric constant of the composites appears almost independent of Li content, while the piezoelectric charge constant of structured composites peaks before the polymorphic phase transition, at 3 mol% of Li. The peak in performance can be attributed to the increased primary particle size of the composition in combination with its single phase orthorhombic crystal structure. The enhancement of the energy harvesting figure of merit, derived from substituting 3 mol% of Li in the KNN particulate, makes these composites an interesting choice for flexible energy generators.     

High and Frequency‐Insensitive Converse Piezoelectric Coefficient Obtained in AgSbO3‐Modified (Li,K, Na)(Nb,Ta)O3 Lead‐Free Piezoceramics

AgSbO₃ was doped into KNN‐based lead‐free piezoceramics with an optimized composition of Li_0.02(Na_0.53K_0.48)_0.98Nb_0.8Ta_0.2O₃ (abbreviated as LKNNT) to further enhance its piezoelectric property. The doping of AgSbO₃ was found to be effective in reducing the grain sizes, resulting in more uniform microstructure in AgSbO₃‐doped LKNNT ceramics. AgSbO₃ lowers tetragonal‐orthorhombic phase transition point (T_T‐O), but with a more gentle rate as compared with other dopants. A large converse piezoelectric coefficient d₃₃* up to 598 pm/V under a relatively low electric field of 1 kV/mm was obtained in the LKNNT‐5 mol% AgSbO₃ composition, whose tetragonal‐orthorhombic phase transition point (T_T‐O) was controlled near room temperature, but its Curie temperature was kept at 235°C. The d₃₃* obtained in the present material is a very high value for nontextured KNN‐based ceramics, which is attributed to the polymorphism phase transition effect and “soft” behavior caused by the addition of AgSbO₃.     

Correlation Between Piezoelectric Properties and Phase Coexistence in (Ba,Ca)(Ti,Zr)O3 Ceramics

High piezoelectric properties are desired for lead‐free piezoelectric materials in consideration as a replacement for lead‐based materials in applications. Due to the high piezoelectric coefficient, (Ba_100?xCa_x) (Ti_100?yZr_y) O₃ (BCTZ) piezoelectric ceramics have been considered as a promising lead‐free alternate piezoelectric material. Here, six compositions were selected based on a prediction that all the compositions would have high piezoelectric coefficient at room temperature. The results confirmed all compositions exhibit well developed hysteresis loops and a large piezoelectric coefficient at room temperature. This is due to the coexistence of several phases where the major phase is likely to be orthorhombic and the second phase is proposed to be tetragonal. The phase transition was found to occur over a broad temperature range instead of at a specific temperature only. A relationship between the tetragonal–orthorhombic phase transition temperature and Ca²⁺ and Zr⁴⁺ content was proposed. This enables clear determination of BCTZ compositions with high piezoelectric coefficient at a desired operation temperature.     

Effects of Bi0.5Na0.5HfO3 addition on the phase structure and piezoelectric properties of (K,Na)NbO3‐based ceramics

Lead‐free perovskite (1‐x)(K_0.48Na_0.48Li_0.04)Nb_0.95Sb_0.05O₃‐x(Bi_0.5Na_0.5)HfO₃ piezoelectric ceramics were prepared by a traditional ceramic fabrication method. An investigation was conducted to assess the effects of (Bi_0.5Na_0.5)HfO₃ content on the crystal structure, microstructure, phase‐transition temperatures, and piezoelectric properties of the ceramics. The X‐ray diffraction results, combined with the temperature dependence of dielectric properties, revealed that the ceramics experienced a structural transition from an orthorhombic phase to a tetragonal phase with the addition of (Bi_0.5Na_0.5)HfO₃, and a coexistence of orthorhombic and tetragonal phases was identified in the composition range of 0.005≤x≤0.015. An obviously improved piezoelectric activity was obtained for the ceramics with compositions near the orthorhombic‐tetragonal phase boundary, among which the composition x=0.005 exhibited the maximum values of piezoelectric constant d₃₃, and planar and thickness electromechanical coupling coefficients (k_p and k_t) of 246 pC/N, 0.435, and 0.554, respectively. Furthermore, the Curie temperature of the ceramics was found decreasing with the increase in (Bi_0.5Na_0.5)HfO₃ content, but still maintaining above 300°C for the phase boundary compositions. These results indicate that the ceramics are promising lead‐free candidate materials for piezoelectric applications.     

(K,Na)NbO3‐Based Lead‐Free Piezoceramics: Fundamental Aspects,Processing Technologies,and Remaining Challenges

Environment‐friendly lead‐free piezoelectric ceramics have been studied extensively in the past decade with great progress particularly in systems based on a niobate perovskite compound formulated as (K, Na)NbO₃ (abbreviated as KNN). A comprehensive review on the latest development of KNN‐based piezoelectric ceramics is presented in this article, including the phase structure, property enhancement approaches, and sintering processes as well as the status of some promising applications. The phase structure of KNN was reexamined and associated with the effect of chemical modification on its tetragonal‐to‐orthorhombic transition. Then, a special focus is placed on the temperature dependence of piezoelectric properties of KNN‐based ceramics, followed by reviewing the recent approaches devoted to the temperature‐stability enhancement. The processing fundamentals related to the sintering of KNN‐based ceramics are also presented with an emphasis on compositional and microstructural control. Finally, this review introduces several industrial attempts of traditional piezoceramic products using KNN‐based ceramics and the studies on some promising application in authors' laboratory.     

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.     

Electric‐Field‐Driven Phase Transition Process in (K,Na, Li)(Nb,Ta, Sb)O3 Lead‐Free Piezoceramics

The electric‐field‐driven phase transition in (K, Na, Li)(Nb, Ta, Sb)O₃ lead‐free piezoelectric ceramics was investigated by X‐ray diffraction, Raman spectra, and the temperature dependences of permittivity spectra. After poling under different electric fields, phase of the ceramics transformed gradually from orthorhombic–tetragonal coexisting phase to orthorhombic phase, indicating that the crystal structure of ceramics was strongly sensitive to electric field as an external stimulus. A secondary phase K₃Li₂Nb₅O₁₅ induced by electric field was detected in the ceramics with Li content of 7 mol%, which was close to the solubility limit of lithium. This field‐induced secondary phase resulted from the movement of Li ions and the structural deformation induced by electric field. Moreover, piezoelectric constant d₃₃ increased with the increasing poling field strength and the enhancement can be attributed to the field‐triggered domain switching. This study implied that in addition to temperature and composition, which has been reported in previous researches, electric field might be an effective way for inducing phase transition in lead‐free piezoelectric ceramics and improving the electrical performances simultaneously.     

The NbO6 octahedral distortion and phase structural transition of Eu3+‐doped K0.5Na0.5NbO3–xLiNbO3 ferroelectric ceramics

A small quantity of Eu³⁺ ions were doped in the lead‐free ferroelectric K_0.5Na_0.5NbO₃–xLiNbO₃ (KNN–xLN, 0 ≤ x ≤ 0.08) ceramics to investigate the NbO₆ octahedral distortion induced by the increasing LN content. In addition, the phase structure, ferroelectric, and photoluminescence properties of K_0.5Na_0.5NbO₃–xLiNbO₃:0.006Eu³⁺ (KNN–xLN:0.006Eu³⁺) lead‐free piezoelectric ceramics were characterized. All the X‐ray diffraction, Raman spectra, dielectric constant vs temperature measurements and the photoluminescence of Eu³⁺ ions demonstrated that the prepared ceramics undergo a polymorphic phase transition (PPT, from orthorhombic to tetragonal phase transformation) with the rising LN content, and the PPT region locates at 0.05 ≤ x ≤ 0.06. The ferroelectric properties, Raman intensity ratios and photoluminescence intensity ratios show similar variations with the increasing LN content, all with a maximum value achieved at the PPT region. We believe that the close relationship among the ferroelectric properties, Raman intensity ratios, and photoluminescence intensity ratios is caused by the NbO₆ octahedral distortion. The photoluminescence of Eu³⁺ ion was discussed basing on the crystal‐symmetry principle and Judd‐Ofelt theory.     

New Lead‐Free (1 − x)(K0.5Na0.5)NbO3–x(Bi0.5Na0.5)ZrO3 Ceramics with High Piezoelectricity

For enhancing the piezoelectric properties of ceramics (Bi_0.5Na_0.5)ZrO₃ (BNZ) was used to partially substitute (K_0.5Na_0.5)NbO₃ (KNN). The addition of BNZ changes the symmetry of KNN ceramics from orthorhombic to tetragonal, and finally to rhombohedral phase. A new phase boundary with both rhombohedral–orthorhombic and orthorhombic–tetragonal phase transitions near room temperature is identified for KNN–0.050BNZ ceramics, where optimum electrical properties were obtained: d₃₃ = 360 pC/N, k_p = 32.1%, ε_r = 1429, tanδ = 3.5%, and T_C = 329°C. The results indicated a new method for designing high‐performance lead‐free piezoelectric materials.     

Phase stability,electronic structures,and superconductivity properties of the BaPb1−xBixO3 and Ba1−xKxBiO3 perovskites

With extensive first‐principles calculations, we investigate the phase stability, electronic structures, and superconductivity properties of the BaPb_1?xBi_xO₃ (BPBO) and Ba_1?xK_xBiO₃ (BKBO) perovskites with the cubic (C), tetragonal (T), and orthorhombic (O) phases. Our calculations show that the tetragonal superconducting phases of both perovskites are metastable. However, the orthorhombic phase of the BPBO perovskite in the superconductivity region is only slightly more stable than the tetragonal phase. The small energy difference between the T and O phases and the discontinuous T‐to‐O phase transition account for the experimentally observed coexistence of the T and O phases. On the other hand, the BKBO perovskite involves a large energy difference between the T and O phases, which induces a low equilibrium temperature of the discontinuous T‐to‐O phase transition, in agreement with the experimental observation that the tetragonal BKBO is maintained down to low temperatures. Moreover, the electronic structures of both BPBO and BKBO superconductors show a flat band near the Fermi level, which is favorable for superconductivity. Furthermore, we find that the longer the total length of the flat band segment is, the higher the critical temperature of the BPBO or BKBO perovskite is. This key finding could be generalized straightforwardly to other unconventional superconductors and can be used to design and find optimal composition with maximum T_c for new unconventional superconductors.     

Investigation on the phase transition behavior and electrical properties of textured Lix(K0.48Na0.52)1−xNbO3 piezoelectric ceramics

Lead-free Li_x(K_0.48Na_0.52)_1−xNbO₃ (KNN–xLi) ceramics were successfully prepared by the tape casting method and solid-state reaction. The effects of Li content on phase transition, microstructure and electrical properties were investigated. XRD results show strong preferred orientation, indicating the presence of textured structure in the samples. With increasing Li content, the Currie Temperature shifts to higher temperature while the phase transition temperature between orthorhombic and tetragonal phases shifts to lower temperature. The sample with x=0.05 is determined to contain two perovskite phases with orthorhombic and tetragonal structures at room temperature, respectively, and exhibits the maximum values of piezoelectric coefficient of 286 pC/N and planar electromechanical coupling factor of 0.45.     

Phase transition,microstructure, and dielectric properties of Li/Ta/Sb co-doped (K,Na)NbO3 lead-free ceramics

Li/Ta/Sb co-doped lead-free (K_0.4425Na_0.52Li_0.0375)(Nb_0.93−xTa_xSb_0.07)O₃ (abbreviated KNLNST_x) piezoelectric ceramics, with Ta-doping ratio of x ranging from 0.0275 to 0.0675, were synthesized using the conventional solid-state reaction method at the sintering temperature of 1130 °C. The effects of Ta content on the microstructure, dielectric properties, and phase transition behavior of the prepared ceramics were systematically investigated. The X-ray diffraction results show that all KNLNST_x ceramics formed a secondary phase, which is assigned to the tetragonal tungsten-bronze type (TTB) structure phase, and showed a phase transition from an orthorhombic symmetry to a tetragonal symmetry across a composition region of 0.0375<x<0.0475. The grain shape and size that correspond to the phase structure transformations can be clearly observed in the scanning electron microscopy images. As x increased to 0.0475, the KNLNST_0.0475 ceramics changed from orthorhombic to tetragonal structure and showed excellent piezoelectric properties of d₃₃=313 pC/N, k_p=47%, and ε_r=1825. By contrast, samples of x=0.0375 with orthorhombic symmetry exhibited poor piezoelectric properties, with d₃₃=200 pC/N and ε_r=1015. These results indicate that phase structure is vital in the piezoelectric properties of KNN lead-free ceramics.     

High‐Performance Small‐Amount Fe2O3‐Doped (K,Na)NbO3‐Based Lead‐Free Piezoceramics with Irregular Phase Evolution

[(K_0.43Na_0.57)_0.94Li_0.06][(Nb_0.94Sb_0.06)_0.95Ta_0.05]O₃ + x mol% Fe₂O₃ (KNLNST + x Fe, x = 0~0.60) lead‐free piezoelectric ceramics were prepared by conventional solid‐state reaction processing. The effects of small‐amount Fe₂O₃ doping on the microstructure and electrical properties of the KNLNST ceramics were systematically investigated. With increasing Fe³⁺ content, the orthorhombic‐tetragonal polymorphic phase transition temperature (T_O‐T) of KNLNST + x Fe ceramics presented an obvious “V” type variation trend, and T_O‐T was successfully shifted to near room temperature without changing T_C (T_C = 315°C) via doping Fe₂O₃ around 0.25 mol%. Electrical properties were significantly enhanced due to the coexistence of both orthorhombic and tetragonal ferroelectric phases at room temperature. The ceramics doped with 0.20 mol% Fe₂O₃ possessed optimal piezoelectric and dielectric properties of d₃₃ = 306 pC/N, k_p = 47.0%, = 1483 and tan δ = 0.023. It was revealed that the strong internal stress in the KNLNST + x Fe ceramics with higher Fe³⁺ contents (x = 0.40, 0.60) stabilized the orthorhombic phase, leading to the irregular “V” type rather than the usually observed monotonic phase transition with composition change in the ceramics.     

Structure‐property relationships in BiScO3–PbTiO3–PbMg1/3Nb2/3O3 ceramics near the morphotropic phase boundary

The phase structure, dielectric, ferroelectric, and piezoelectric properties of (1?2x)BiScO₃–xPbTiO₃–xPbMg_1/3Nb_2/3O₃ ceramics (x = 0.30‐0.46) were studied. It was found that an increase in x leads to a structural phase transition between the rhombohedral and tetragonal phase via an intermediate monoclinic phase and to a crossover from the nonergodic relaxor state to the ferroelectric one. It was proposed that at x > 0.42 the phase transition changes from second to first order. The assumption about the existence of a tricritical point on the phase diagram at x ≈ 0.42 with the enhanced dielectric response has been made. The observed structure‐property relationships of the studied solid solutions are discussed. It is shown that the solid solutions with x = 0.42 are characterized by the high piezoelectric parameters (d₃₃ = 509 pC/N, d₃₁ = ?178 pC/N, d_h = 153 pC/N), which makes possible their applications in sonar equipment.     

Domain Structure of Poled (K0.50Na0.50)1−xLixNbO3 Ceramics with Different Stabilities

Domain structure of several poled (K_0.50Na_0.50)_1?xLi_xNbO₃ ceramics (with chemical compositions of x = 0.03, 0.065, and 0.08, respectively) was investigated by means of observing the domain patterns with an acid‐etching technique. Among the three ceramics, the one with x = 0.03 is of orthorhombic phase and the other two are of tetragonal phase at room temperature. It was found that these ceramics possess distinctly different features of domain patterns and show a large difference in the time‐aging stability of piezoelectric properties. For the ceramic with x = 0.03, domain patterns consist of simply one single set or a few sets of parallel stripes inside the polycrystalline grains. In contrast, for those with x = 0.065 or 0.08, herringbone‐type patterns and a large number of watermarks are additionally observed. Furthermore, the ceramic with x = 0.03 was confirmed to have a much better time‐aging stability of piezoelectric properties than the other two. The results indicate that domain structure is more stable in orthorhombic phase than in tetragonal phase.     

Investigation of the Structure and Electrical Properties of (KxNa0.96−xLi0.04)(Nb0.96−yTaySb0.04)O3 Piezoelectric Ceramics Modified with Manganese

The effect of high doping levels of manganese (Mn) on the structure and electrical properties of (K_xNa_1?x)NbO₃ (KNN) ceramics containing Li, Ta, and Sb has been investigated. The samples were measured using synchrotron X‐ray diffraction whereas Rietveld refinement with Fullprof was used to determine the structural information as a function of temperature. Temperature‐dependent dielectric measurement was used to compare the phase transition temperatures. The results show that Mn decreases the temperature range of phase coexistence between the orthorhombic and tetragonal phase from ~180°C to ~120°C. The Curie temperature remained unchanged with Mn addition while the dielectric constant and dielectric loss increased with Mn addition. High amounts of Mn led to a reduction in both piezoelectric and ferroelectric properties. The remnant polarization, remnant strain, and piezoelectric coefficient values decreased from 24 μC/cm², 0.000824, 338 ± 37 pm/V to 13 μC/cm², 0,00014 and 208 ± 27 pm/V, respectively for the undoped and 5 mol% Mn‐doped sample.     

Polarization switching and rotation in KNN-based lead-free piezoelectric ceramics near the polymorphic phase boundary

(K,Na)NbO₃ (KNN)-based ceramics have attracted considerable attention owing to their excellent piezoelectric performance in the polymorphic phase boundary (PPB); however, many researchers have found that the optimal composition usually appears on the tetragonal side near the PPB zone. In this study, it is found that the maximum piezoelectric performance is achieved in the PPB region for unpoled ceramics due to the more efficient and facile polarization switching. However, the most outstanding piezoelectricity shifts to the tetragonal side after the ceramics are poled. Raman spectra and first-principles calculations reveal the occurrence of a phase transformation from a tetragonal to monoclinic structure under an external electric field. Hence, the unpoled tetragonal ceramics transform to a two-phase coexistence condition after the poling process and exhibit the best electrical properties driven by the combined effects of polarization switching and rotation. This study reveals that the electric-field-induced phase transformation leads to the optimal composition on the tetragonal side, and this can provide useful guidance for the design of high-performance KNN-based materials.     

Strain effects of temperature and electric field induced phase instability in (Na,K)(Nb,Sb)O3-LiTaO3 lead-free ceramics

The temperature and electric field induced phase instability were found to produce distinctly different temperature-dependences of small- and high-field strains in the proximity of orthorhombic (O) to tetragonal (T) polymorphic phase transition of (Na,K)(Nb,Sb)O₃-LiTaO₃ lead-free ceramics. As evidenced by means of in-situ and ex-situ synchrotron x-ray diffraction and quantitative analyses, both O-T phase coexistence and intermediate monoclinic (M_c) phase were believed to promote intrinsic piezoelectric strains. Further increase of high-field strains with temperature was ascribed to enhanced contributions from field-induced reversible M_c-T phase transition, plus little extrinsic contribution from non-180° domain switching which was unexpectedly hindered near the phase boundary.     

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.     

Domain Structure Evolutions During the Poling Process for [011]‐Oriented PMN–xPT Crystals Across the MPB Region

The poling effect on the [011]‐oriented (1?x)Pb(Mg_1/3Nb_2/3)O₃‐xPbTiO₃ (PMN–xPT) single crystals across the morphotropic phase boundary (MPB) was studied. The dielectric and piezoelectric properties were investigated as a function of the poling field. Domain structure evolutions during the poling process were recorded. In the unpoled PMN–xPT phase diagram, an apparent rhombohedral (R)‐tetragonal (T) phase boundary exists. With room‐temperature poling, the structure transformation sequence strongly depends on the composition. The crystal experiences a direct transition to the 2R/2T domain state in the rhombohedral or tetragonal phase field beyond the MPB region, whereas within the MPB zone it is hard to achieve the 2R/2T engineered configuration although the initial state is either rhombohedral or tetragonal as well. The piezoelectric responses of the MPB·PMN–xPTs are extraordinary weak (d₃₃ ~ 250 pC/N), in contrast to the [011]‐oriented multidomain PMN–xPTs with ultrahigh‐piezoelectric coefficient (d₃₃ > 1000 pC/N). We demonstrate that a slight composition variation near the MPB will significantly influence the domain evolution route and piezoelectricity for the [011]‐oriented PMN–xPT crystals. We also confirm the feasibility to realize the 2R/2T engineered domain configuration for the [011]‐oriented MPB crystals, which will extend the desired portion of the Bridgeman‐grown boules with optimal piezoelectric properties.