Phase structure and enhanced piezoelectric properties in (1-x)(K0.48Na0.52)(Nb0.95Sb0.05)O3-x(Bi0.5Na0.42Li0.08)0.9Sr0.1ZrO3 lead-free piezoelectric ceramics

The piezoelectric properties of KNN lead-free piezoelectric ceramics could be greatly enhanced by forming multiphase coexistence. In this work, binary system (1-x)(K_0.48Na_0.52)(Nb_0.95Sb_0.05)O₃-x(Bi_0.5Na_0.42Li_0.08)_0.9Sr_0.1ZrO₃ [(abbreviated as (1-x)KNNS-xBNLSZ] ceramics with rhombohedral-tetragonal (r-T) phase boundary was designed and synthesized using the conventional solid-state sintering method, and effects of BNLSZ contents on their micrograph, phase structure and electrical properties were also investigated. According to phase diagram from the results of temperature-dependent capacitance and dielectric constant, the ceramics exhibit the R-T phase coexistence in the composition range of 3.5%≤x<4.5%, and an enhanced dielectric, ferroelectric, and piezoelectric behavior was obtained at such a phase boundary zone. As a result, the ceramics with x=0.04 exhibit optimum electrical properties of d₃₃~461 pC/N, k_p~46%, tan δ~0.03, P_r~16.9 μC/cm², and E_c ~9 kV/cm, together with a Curie temperature (T_C) of ~228 °C. Such a good comprehensive performance obtained in this present work is due to the R-T phase transition and enhanced ɛ_rP_r. It was believed that this ceramic system would promote the development of KNN-based lead-free ceramics.     

Room temperature constructing rhombohedral-tetragonal phase boundary in novel (Bi,Na)(Zr,Ti)O3 modified (K,Na)(Nb,Sb)O3 ceramics: Phase structure,defect and piezoelectric performance

Lead-free (1-x)(K_0.5Na_0.5)(Nb_0.96Sb_0.04)O₃-x(Bi_0.5Na_0.5)(Zr_0.8Ti_0.2)O₃ ceramics (abbreviated as (1-x)KNNS-xBNZT, x = 0, 0.01, 0.02, 0.03, 0.035 and 0.04) were synthesized by the solid-state method, and the dependence of phase evolution, microstructure, oxygen vacancy defect and electrical properties on compositions were carefully investigated. All ceramics had a pure perovskite structure and a dense microstructure. The phase transition temperatures (T_R-O and T_O-T) of the ceramics were adjusted by adding BNZT, and the rhombohedral-tetragonal (R-T) phase coexistence boundary was successfully constructed at room temperature when x = 0.03, the excellent piezoelectric performance (d₃₃ ～ 323 pC/N, k_p ～ 0.372) and high Curie temperature (T_C ～ 276 °C) have been achieved at this time. The grain size of the ceramics showed a strong difference on x content, and the maximum relative density value of 95.42% was obtained. The domain structure characterized by PFM confirmed that the ceramics possess small-sized nano-domains and complex domains at x = 0.03, which are the origin of enhanced piezoelectric properties. Moreover, the oxygen vacancy defect that can pin the domain walls was increased with the addition of (Bi_0.5Na_0.5)(Zr_0.8Ti_0.2)O₃. As a result, the doping with BNZT can significantly affect the phase structure and electrical properties of the ceramics, indicating that the (1-x)KNNS-xBNZT ceramics system with a R-T phase boundary is a promising lead-free piezoelectric material.     

Enhanced electromechanical properties of CaZrO3-modified (K0.5Na0.5)NbO3-based lead-free ceramics

Pairing of large strain response and high d₃₃ with high T_c in (K_0.5Na_0.5)NbO₃-based materials is of high significance in practical applications for piezoelectric actuators. Here, we report remarkable enhancement in the electromechanical properties for (1-x)(K_0.52Na_0.48) (Nb_0.95Sb_0.05)O₃-xCaZrO₃ (KNNS-xCZ) lead-free ceramics through the construction of a rhombohedral (R)-tetragonal (T) phase boundary. We investigated the correlation between the composition-driven phase boundary and resulting ferroelectric, piezoelectric, and strain properties in KNNS-xCZ ceramics. The KNNS-xCZ ceramics with x=0.02 exhibited a large strain response of 0.23% while keeping a relatively large d₃₃ of 237pC/N, which was mainly ascribed to the coexistence of R and T phases confirmed by the XRD and dielectric results. It was found that pairing of large strain response and high d₃₃ in KNN-based materials was achieved. As a consequence, we believe that this study opens the possibility to achieve high-performance lead-free electromechanical compounds for piezoelectric actuators applications.     

Multiphase coexistence and enhanced electrical properties in (1-x-y)BaTiO3-xCaTiO3-yBaZrO3 lead-free ceramics

In this work, the multiphase coexistence of rhombohedral-orthorhombic and orthorhombic-tetragonal (R-O/O-T) was constructed in (1-x-y)BaTiO₃-xCaTiO₃-yBaZrO₃ ceramics with 0.14 ≤ x ≤ 0.16 and 0.10 ≤ y ≤ 0.12, and thus a large piezoelectric constant (d₃₃) of 600 pC/N was attained in the ternary (1-x-y)BaTiO₃-xCaTiO₃-yBaZrO₃ ceramics using the optimization of x and y. The R-O/O-T multiphase coexistence as well as the enhancement of dielectric and ferroelectric properties can be responsible for the high d₃₃ of this work. In addition, a high strain of 0.15% was observed in the multiphase coexistence. As a result, electrical properties of BaTiO₃ can be optimized by the construction of multiphase coexistence through the co-doping of CaTiO₃ and BaZrO₃.     

Processing and enhanced electrical properties of Sr1-x(K0.5Bi0.5)xBi2Nb2O9 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics, Sr_1−x(K_0.5Bi_0.5)_xBi₂Nb₂O₉ (SKBN-x, x=0, 0.2, 0.5, 1.0), were synthesized by a conventional solid-state reaction. Structural and electrical properties of SKBN-x ceramics were investigated. X-ray diffraction analysis suggested that the substitution led to the formation of a layered perovskite structure. Plate-like morphologies for the grains were clearly observed in all the samples, which are characteristic for layer-structure Aurivillius compounds. The Curie temperature (T_c) is found to shift to higher temperature from 445 °C to 509 °C with increasing (K, Bi) content. Excellent remanent polarization (2P_r∼15 μC/cm²) were obtained for SKBN-0.2 ceramic. High piezoelectric coefficient of d₃₃∼21  pC/N were obtained for the samples at x=0.5. Additionally, thermal annealing studies indicated that the piezoelectric coefficient (d₃₃) of SKBN-0.5 was unchanged even if annealing temperature increased to be 450 °C, demonstrating the ceramics are the promising candidates for high-temperature applications.     

High performance lead-free piezoelectric 0.96(K0.48Na0.52)NbO3-0.03[Bi0.5(Na0.7K0.2Li0.1)0.5]ZrO3-0.01(Bi0.5Na0.5)TiO3 single crystals grown by solid state crystal growth and their phase relations

0.96(K_0.48Na_0.52)NbO₃-0.03[Bi_0.5(Na_0.7K_0.2Li_0.1)_0.5]ZrO₃-0.01(Bi_0.5Na_0.5)TiO₃ single crystals were grown for the first time by the solid state crystal growth method, using [001] or [110]-oriented KTaO₃ seed crystals. The grown single crystal shows a dielectric constant of 2720 and polarization-electric field loops of a lossy normal ferroelectric, with P_r = 45 μC/cm² and E_c = 14.9 kV/cm, while the polycrystalline samples with a dielectric constant of 828 were too leaky for P-E measurement due to humidity effects. The single crystal has orthorhombic symmetry at room temperature. Dielectric permittivity peaks at 26 °C and 311 °C, respectively, are attributed to rhombohedral-orthorhombic and tetragonal–cubic phase transitions. Additionally, Raman scattering shows the presence of an orthorhombic-tetragonal phase transition at ∼150 °C, which is not indicated in the permittivity curves but by the loss tangent anomalies. A transition around 700 °C in the high temperature dc conductivity is suggested to be a ferroelastic-paraelastic transition.     

Dielectric and impedance spectroscopy analysis of lead-free (1-x)(K0.44Na0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3-xBaTiO3 ceramics

(1-x)(K_0.44Na_0.52Li_0.04)(Nb_0.86Ta_0.10Sb_0.04)O₃-xBaTiO₃ (labeled as (1-x)KNLNTS- xBT, x = 0.00, 0.02, 0.04, 0.06, 0.08, 0.10) lead-free ceramics were prepared by a solid-state sintering method. As the BT content increased, the phase of ceramics changed from orthorhombic (0.00 ≤ x ≤ 0.02) to orthorhombic-tetragonal (0.02 < x < 0.06) structure, and finally turned into tetragonal (0.06 ≤ x ≤ 0.10) structure. The Curie-Weiss law and modified Curie-Weiss law were applied to analyzing dielectric properties. With the increase of BT content, the relaxation degree increased, which indicated that the ceramics shown a excellent relaxation behavior. For 0.9KNLNTS- 0.1BT ceramics, the dispersion coefficient γ reached the maximum of 1.73, which is hugely attractive for lead-free relaxor ferroelectrics. From its variation of impedance spectroscopy with temperature, it was found that the relaxation and conduction behavior were associated with the thermal activation, and the oxygen vacancies were the potential ionic carriers. Moreover, through Arrhenius fitting, the activation energy of 0.9KNLNTS- 0.1BT ceramic was 0.82(6) eV, indicating that the oxygen vacancy concentration for the ceramics was high.     

High-temperature dielectric and energy storage properties of Bi0.5Na0.5TiO3-based ceramics modified by Sr0.8Na0.4Nb2O6

Sr_0.8Na_0.4Nb₂O₆ with a tungsten bronze structure is introduced into perovskite-structured 0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ composition (abbreviated as BNT-BT-xSNN, x = 0-0.04). The temperature stability of dielectric properties and energy storage performance is found to be effectively enhanced by Sr_0.8Na_0.4Nb₂O₆ dopant. When x is 0.03, the temperature ranges covering |ε'-ε'_150°C|/ε'_150°C ≤15% and tanδ ≤ 0.02 are 43°C-404°C and 90°C-422°C, respectively. More importantly, ε′ can be retained as high as 3304 at 150°C. Besides, the variances of energy storage density and its efficiency are 6.4% and 5.3%, respectively, in the temperature range from room temperature (RT) to 180°C. Therefore, this work provides a new method of compositional modification in BNT-based materials to improve their temperature stability of dielectric and energy storage properties.     

(Bi0.5Na0.5)ZrO3 modified KNN-based ceramics: Enhanced electrical properties and temperature insensitivity

To further improve the properties of KNN-based lead-free ceramics, a new ceramic system, (0.98-x)K_0.525Na_0.475Nb_0.965Sb_0.035O₃-0.02 BaZr_0.5Hf_0.5O₃-x(Bi_0.5Na_0.5)ZrO₃(KNNS-BZH-xBNZ) was designed, the relevant properties such as piezoelectricity, strain, and temperature stability were analysed in detail. It was found that the R-T phase boundary can be successfully constructed when x=0.030, and this two-phase coexistence shows relatively good comprehensive properties (d₃₃~410 pC/N, T_C~255 °C, S_uni~0.132%, and d₃₃*~441 pm/V). Meanwhile, its strain property also shows good temperature stability from room temperature to 180 °C (S_uni100°C/S_uniRT~97.5% and S_uni180°C/S_uniRT~83.9%), which is comparatively superior to many KNN-based ceramics and some lead-based ceramics. Therefore, KNNS-BZH-xBNZ ceramics may broaden the practical application of lead-free ceramics.     

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.     

Ag2O掺杂对Li0.02(Na0.52K0.48)0.98Nb0.8Ta0.2O3无铅压电陶瓷电性能影响的研究

用传统的固相无压烧结法制备了Li0.02(Na0.52K0.48)0.98Nb0.8T0.2O3-xAg2O(0≤x≤0.1)无铅压电陶瓷,研究了Ag2O掺杂对陶瓷电性能的影响.研究发现,适当掺杂Ag2O能显著提高陶瓷的电性能,在1090℃的烧结温度下,当掺杂量为0.06时,陶瓷的压电性能最佳,d33、Kp、εr、Pr均达到最大(d33=229 pC/N,Kp=55.2％,εr=802,Pr=23 μC/cm2),矫顽场降到最低(Ec=12 kV/cm),应变达到2.0％.但Ag2O的添加使陶瓷的机械品质因数Qm由139.7降到了58.8,使介电损耗tanδ由1.38％增加到了2.7％.     

（1－x）Bi0．5（Na0．8K0．2）0．5TiO3－xKSbO3压电陶瓷的制备及性能研究

采用传统固相法制备了新型（1－x）Bi0．5（Na0．8K0．2）0．5TiO3－xKSbO3无铅压电陶瓷,利用XRD、 SEM等测试技术表征了该陶瓷的晶体结构、表面形貌、压电和介电性能。研究结果表明,在所研究的组成范围内陶瓷材料均能形成纯的钙钛矿固溶体。在室温下,当KSbO3的掺杂量为1％时,该体系表现出较好的介电性能：εr和tanδ分别为2231和0．055。     

Enhanced energy storage properties of {Bi0.5[(Na0.8K0.2)1-zLiz]0.5}0.96Sr0.04(Ti1-x-yTaxNby)O3 lead-free ceramics

Energy storage properties of {Bi_0.5[(Na_0.8K_0.2)_1-zLi_z]_0.5}_0.96Sr_0.04(Ti_1-x-yTa_xNb_y)O₃ (BNKLSTTN-x/y/z) lead-free ceramics are investigated. It is found that Ta performs better than Nb in the case of their energy storage density values, and the addition of optimum Li contents can enhance the energy storage properties by enhancing the dielectric breakdown strength (DBS). Enhanced energy storage density of 1.60 J/cm³ under a low electric field of 90 kV/cm is achieved in BNKLSTTN-0.025/0/0.10 samples, and the fatigue-free properties are also observed. In addition, the BNKLSTTN-0.025/0/0.10 samples show the enhanced temperature dependence of energy storage density. These results indicate that the BNKLSTTN-x/y/z ceramics are one of the most promising lead-free materials for energy storage applications.     

Phase transition behavior and electrical properties of (1 − x)Bi0.5Na0.5TiO3–x(Na0.53K0.44Li0.04)(Nb0.88Sb0.08Ta0.04)O3 lead-free ceramics

(1 ? x)Bi_0.5Na_0.5TiO₃–x(Na_0.53K_0.44Li_0.04)(Nb_0.88Sb_0.08Ta_0.04)O₃ (BNT–xNKLNST) with x = 0–0.10 lead-free piezoelectric ceramics were prepared by a solid state method, and the structure and electrical properties were investigated in this study. It is found that a morphotropic phase boundary (MPB) of rhombohedral (R) and tetragonal (T) phase exists in the range of 0.03 ≤ x ≤ 0.05 and the structure changes to paraelectric phase when x > 0.07. The samples with x = 0.05 exhibit improved electrical properties owing to the formation of MPB, which are as follows: piezoelectric constant d₃₃ = 120 pC/N, remnant polarization P_r = 39.4 μC/cm² and coercive field E_c = 3.6 kV/mm. These results indicate that the enhanced piezoelectric properties for BNT can be achieved by forming the coexistence of R and T phase.     

Electric aging behavior of lead-free Li0.06(K0.48Na0.52)0.94(Nb0.86Ta0.08Sb0.06)O3 piezoelectric ceramics improved by pre-calcined method

In order to improve the piezoelectric and aging properties of the lead-free Li_0.06(K_0.48Na_0.52)_0.94(Nb_0.86Ta_0.08Sb_0.06)O₃ piezoelectric ceramics, the conventional solid-state reaction method and the B-side pre-calcined method were achieved and compared in this paper. The physical and electrical properties of the lead-free Li_0.06(K_0.48Na_0.52)_0.94(Nb_0.86Ta_0.08Sb_0.06)O₃ piezoelectric ceramics material were investigated and discussed. For the B-side pre-calcined method, the ceramic material exhibited the excellent electrical and piezoelectric parameters. Finally, the electromechanical coupling factors, the resonance frequencies, and the resonance resistances of the lead-free ceramic materials were also discussed.     

Thermally stable high strain and piezoelectric characteristics of (Li,Na, K)(Nb,Sb)O3-CaZrO3 ceramics for piezo actuators

The 0.97(Na_0.5K_0.5)(Nb_1−xSb_x)O₃-0.03CaZrO₃ ceramic with x = 0.09 exhibits a high d₃₃ of 518 pC/N and a strain of 0.13% at 4.0 kV/mm owing to its orthorhombic-pseudocubic polymorphic phase boundary (PPB) structure. However, these values decreased considerably above 90°C owing to its low Curie temperature (T_C), indicating that its thermal stability is not sufficient for practical applications. Li₂O was added to the specimen with x = 0.11 to improve its thermal stability of the strain and d₃₃ by increasing the T_C without degrading the actual d₃₃ and strain values. The 0.97(Li_0.04Na_0.46K_0.5)(Nb_0.89Sb_0.11)O₃-0.03CaZrO₃ ceramic, having an orthorhombic-tetragonal PPB structure, exhibits a d₃₃ of 502 pC/N and a strain of 0.16%. This large strain was maintained up to 150°C and the d₃₃ slightly decreased to 475 pC/N at 130°C. Therefore, this lead-free ceramic displays excellent piezoelectric characteristics with improved thermal stability, indicating that it can be applied to piezoelectric actuators.     

Influence of B-site compositional homogeneity on properties of (K0.44Na0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3-based piezoelectric ceramics

The effect of B-site compositional homogeneity on microstructure, piezoelectric properties and dielectric behaviour of lead-free piezoelectric ceramics, (K_0.44Na_0.52Li_0.04) (Nb_0.86Ta_0.10Sb_0.04)O₃, is investigated. The B-site compositional homogeneity is evaluated by using an intermediate precursor obtained by solid state reaction between adequate amounts of Nb₂O₅, Ta₂O₅ and Sb₂O₅, calcined at 1350 °C and attrition milled. The B-site precursor powder is mixed with alkaline carbonates to synthesize perovskite powders and, finally, sinter piezoceramics. X-ray diffraction and Raman spectroscopy reveal the formation of a perovskite phase, although tetragonal tungsten-bronze structure is detected as minor secondary phase. Ceramics processed by using B-site precursor show different crystalline structure as a function of sintering conditions or K/Na ratio. The B-site precursor route produces thus lower piezoelectric properties, but the control of alkali volatilization by using sintering powder bed resulted in a relevant decrease of dielectric losses that favours the d₃₃ enhancement.     

Enhanced piezoelectric properties and low electrical conductivity of Ce-doped Bi7Ti4.5W0.5O21 intergrowth piezoelectric ceramics

New types of Ce-doped Ce_xBi_7-xTi_4.5W_0.5O₂₁ (BTW-BIT-xCe) Aurivillius intergrowth ceramics with high Curie temperatures were synthesized to improve the piezoelectric performances as well as the conduction behaviour, and these ceramics exhibit great potential for high-temperature lead-free piezoelectric applications. The crystal structure, electrical properties and conduction behaviour of BTW-BIT-xCe samples were analysed thoroughly. The XRD patterns combined with Rietveld refinements of the patterns showed that the crystal structure transformed from orthorhombic structure towards pseudo-tetragonal structure with increasing CeO₂ dopant, indicating that a higher symmetry was obtained. The dielectric properties of Ce-doped samples were improved, accompanied by a significant drop in the dielectric loss and a slight decreased Curie temperature (705 °C–683 °C). An enhanced piezoelectric constant d₃₃ of 25.3 pC/N was obtained in BTW-BIT-0.12Ce, which may be attributed to a common decrease in the electrical conductivity and coercive field. Besides, a low electrical conductivity of 2 × 10^-6 S/cm at 540 °C was achieved in the same component owing to a decreased concentration of the oxygen vacancies, which was verified by analyses on XPS spectra. The above results indicate that Ce-doped BTW-BIT samples have great development potential for high temperature piezoelectric applications.     

Li2O excess (Na0.51K0.47Li0.02)(Nb0.8Ta0.2)O3 lead free piezoelectric ceramics

1 mol% Li₂O excess (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ ceramics were prepared by the conventional mixed oxide method and sintered from 950 to 1200 °C. Also, Li₂O was employed as a sintering aid for high densification and low temperature sintering process. X-ray diffraction results of 1 mol% Li₂O excess (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ lead free piezoelectric ceramics indicated that the specimens were well crystallized and have tetragonal structure. The specimens which sintered at 1050 °C showed the highest piezoelectric properties compared with others. The measured piezoelectric constant and electromechanical coupling coefficient were 231 pC/N and 38.9%, respectively. Curie temperature of (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ ceramics was 344.32, 344.4 and 344.5 °C at 1, 10 and 100 kHz, respectively.     

Dielectric temperature stability of Nb-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

In this study, the phase structure, microstructure and dielectric properties of Bi_0.5(Na_0.78K_0.22)_0.5(Ti_1-xNb_x)O₃ lead-free ceramics prepared by traditional solid phase sintering method were studied. The second phase pyrochlore bismuth titanate (Bi₂Ti₂O₇) was produced in the system after introduction of Nb⁵⁺. The dielectric constant of the sample (x = 0.03) sintered at 1130 °C at room temperature reached a maximum of 1841, and the dielectric loss was 0.045 minimum. It had been found that the K⁺ and Nb⁵⁺ co-doped Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics exhibited outstanding dielectric-temperature stability within 100–400 °C with T_cc ≤±15%. Result of this research provides a valuable reference for application of BNT based capacitors in high temperature field.