Na0.5Bi0.5TiO3基无铅压电陶瓷研究与应用的新进展

综述了钙钛矿结构的Na0.5Bi0.5TiO3(简称BNT)基无铅压电陶瓷的研究现状,并与其它无铅基压电陶瓷进行了对比.列举了近年来BNT 基压电陶瓷的新发展和热门体系,结合笔者承担的相关研究工作内容,总结和指出了BNT基无铅压电陶瓷新的研究思路和相关方向.     

（Na0.8K0.2）0.5Bi0.5TiO3-xSrTiO3-0．3％Mn无铅压电陶瓷的结构与性能

采用固相法制备了（Na1-xKx0.5）Bi0.5YiO3-xSrTiO3-0.3Mn系无铅压电陶瓷,研究了该系统的微观结构和压电性能。XRD分析表明所得陶瓷样品在室温下均为三方、四方共存的钙钛矿结构,随着Sr的增加,三方相减少,四方相增加。SEM图谱显示各样品颗粒均匀、具有规则的外形、晶界明显,并且少量Sr的加入使样品更加致密化。该体系样品具有优异的压电性能,在Sr含量为0．02时,压电常数如、平面机电耦合系数k,和厚度机电耦合系数kt同时达到最大值,分别为171pC·N^-1、33．1％和30．5％,Sr具有“软性”添加物的作用     

Bi0.5Na0.5TiO3基无铅压电陶瓷设计与制备研究的新进展

综述了Bi0.5Na0.5TiO3(BNW)基无铅压电陶瓷体系研究的最新进展,介绍了BNT基无铅压电陶瓷的设计方法及其制备技术.用自洽场离散变分法(self-consult charge-discrete variation-Xa,SCC-DV-Xa)等计算方法可为设计新型BNT基陶瓷提供重要的理论指导.用湿化学法,包括:溶胶-凝胶法、柠檬酸盐法、水热法等,可以合成BNT基纳米粉体,该类方法制备的BNT基粉体具有良好烧结活性,利于致密化烧结,使材料电性能得到改善.用模板晶粒生长技术可获得晶粒生长定向程度很高的BNT基压电陶瓷材料,进而提高材料在特定方向的压电性能.     

Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3系无铅压电陶瓷的制备工艺研究

利用XRD、SEM等分析技术 ,研究了Na0 .5Bi0 .5TiO3 -K0 .5Bi0 .5TiO3 系无铅压电陶瓷的合成温度 ,烧成工艺条件对陶瓷晶体结构、压电性能的影响。结果表明 ,合成温度提高有利于主晶相的形成 ,适当延长保温时间有利于材料的压电性能。该体系随着KBT含量的增加 ,烧结温度提高 ,烧结温度范围变窄。同时研究了极化工艺条件对材料压电性能的影响表明 ,提高极化电场和适当提高极化温度有利于压电性能的提高 ,但过高的温度由于受到材料高温下退极化的影响而导致材料压电性能变差     

常压溶剂热法制备Bi0.5Na0.5TiO3纳米粉体的研究

以Bi(NO3)3·5H2O、Ti(OC4H9)4为原料,无水乙醇作溶剂,采用溶剂热法在常压下合成了Bi0.5Na0.5TiO3(简称为BNT)纳米粉体.通过X射线衍射(XRD)和扫描电子显微镜(SEM)对BNT粉体进行了表征.并在常压溶剂热条件下研究了影响BNT晶体生长和形貌的主要因素.实验结果表明:反应温度为100 ℃,保温时间为2.5 h,NaOH浓度为12 mol·L-1,650 ℃下煅烧2 h时,能制备出单一的BNT粉体,且制得粉体的粒径尺寸约为100 nm.     

(K0.5Na0.5)NbO3基无铅压电陶瓷的应用研究

随着人类社会可持续发展战略的全面实施,(K,Na)NbO3基无铅压电陶瓷以其优越的压电性能和较高的居里温度受到人们的广泛关注.本文分析并评述了其国内外的应用近况,尽管(K,Na)NbO3基无铅压电陶瓷取得了较大的进展,但总体上还不能与铅基体系相媲美.因此,(K,Na)NbO3基体系的性能和应用要达到铅基压电陶瓷的水平,还需进行大量的研发工作.     

La掺杂(Na0.5Bi0.5)0.82(K0.5Bi0.5)0.18TiO3系统无铅压电陶瓷的制备工艺探讨

采用传统陶瓷工艺，研究了制备[（Na0.5Bi0.5）0.82（K0.5Bi0.5）0.18]1-xLaxTiO3（x=0．00，0．01，0．03，0．05，0．10）无铅压电陶瓷的工艺条件对陶瓷的物相组成、显微结构和压电性能的影响。利用XRD、SEM等技术分析结果表明，合成温度的提高有利于主晶相的形成，且此系统烧成温度范围较窄，故需控制在合适的烧成温度下才能得到高致密度的陶瓷。同时，研究了极化工艺条件对材料压电性能的影响，结果表明，提高极化电场强度、控制适当的极化温度有利于提高材料的压电性能。     

Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3系无铅压电陶瓷的极化工艺研究

主要研究了极化电场,极化时间和极化温度等工艺参数对Na0.5Bi0.5TiO3-K0.5Bi0.5TiO3系无铅压电陶瓷介电和压电性能的影响。结果表明:极化电场和极化温度对压电陶瓷的介电、压电性能影响较大,而极化时间则影响较小。适宜的极化电场是3～3.5kV/mm,极化温度70～80℃,极化时间为10～15min。     

Y2O3掺杂对(Bi0.5Na0.5)0.94Ba0.06TiO3无铅压电陶瓷性能的影响研究

采用传统固相反应法制备了Y2O3掺杂(Bi0.5Na0.5)0.94Ba0.06TiO3(简写为BNBT6)陶瓷[简称为BNBT6-x(wt%)Y2O3陶瓷].研究了Y2O3 (0.2wt%～0.8wt%)掺杂对BNBT6陶瓷的结构、介电、压电、铁电性能的影响.结果表明,所有Y2O3掺杂陶瓷样品均形成了单一的钙钛矿结构;陶瓷的介电、压电、铁电性能受Y2O3掺杂的影响较为显著:当掺杂0.4wt%Y2O3时,10 kHz频率下测得的室温εr达到1530,且tanδ较小,为0.050,d33达到152 pC/N,kp=0.27,Qm=134.掺杂0.2wt%的Y2O3时BNBT6陶瓷的d33为145 pC/N,kp增大到0.29,Qm达到173,tanδ为0.053;掺杂适量Y2O3的BNBT6陶瓷铁电性能也得到改善.     

(Bi1/2Na1/2)TiO3-BaTiO3系无铅压电陶瓷结构与性能的研究

采用XRD,SEM,HRTEM等分析技术对(1-x)(Bi1/2Na1/2)TiO3-xBaTiO3(简称为BNBT)(x为0.04,0.06,0.08,0.10)进行了结构与性能的研究,并主要分析了x为0.06,即0.94(Bi1/2Na1/2)TiO3-0.06BaTiO3(简称为BNBT6)在不同烧结温度下的结构形态及其对性能的影响.结果表明:(1-x)(Bi1/2Na1/2)TiO3-xBaTiO3系统具有很窄的烧结范围.另外,加入过量的Ba2+,能起到阻碍晶粒长大的作用.     

掺杂Co2O3对Na0．5Bi0.5TiO3基压电陶瓷性能的影响

通过固相法合成Na0.5Bi0.5TiO3+xmol%Co3+(简写为:NBT-xC)体系无铅压电陶瓷,并对其相结构、压电、介电及铁电性能进行了研究.XRD分析结果表明,所有组成均形成三方钙钛矿结构.SEM扫描电镜照片显示Co2O3的引入有利于晶粒长大,提高致密度.随着Co含量的增加,陶瓷的压电常数d33,机电耦合系数Kp都略有下降,机械品质因素Qm有明显提高,在x=3时达到极大值:0m-934,同时介电损耗出现极小值:tgδ=0.02(1kHz),综合得出Co离子起"硬性掺杂"作用.     

High-energy storage density in NaNbO3-modified (Bi0.5Na0.5)TiO3-BiAlO3-based lead-free ceramics under low electric field

Ceramic-based dielectric capacitor are highly suitable for pulsed power applications due to their high power density and excellent reliability. However, the ultrahigh applied electric field limit their applications in integrated electronic devices. In this work, (1−x){0.96(Bi_0.5Na_0.5)(Ti_0.995Mn_0.005)O₃-0.04BiAlO₃}-xNaNbO₃ (BNT-BA-xNN, x = 0, 0.04, 0.08, 0.12, and 0.16) ternary ceramics were designed to achieve excellent energy storage properties. It was found that the introduction of NaNbO₃ (NN) effectively increase the difference (ΔP) between P_max and P_r, resulting in an obvious enhancement of the energy storage properties. High recoverable energy storage density, responsivity, and power density, that is, W_rec = 2.01 J/cm³, ξ = W_rec/E = 130.69 J/(kV⋅m²), and P_D = 25.59 MW/cm³, accompanied with superior temperature stability were realized at x = 0.14 composition. In addition, the thermal stable dielectric properties of the sample can be prominently improved with increasing NN content. The temperature coefficient of capacitance (TCC) of x = 0.16 composition is lower than 15% over the temperature range from 49°C to 340°C, with a high dielectric permittivity of 1647 and a low dielectric loss (0.0107) at 150°C. All these features show that the BNT-BA-xNN ceramics are promising materials for energy storage application.     

Luminescence and electrical properties of Eu-modified Bi0.5Na0.5TiO3 multifunctional ceramics

The Eu³⁺-modified Bi_0.5Na_0.5TiO₃ (BNT) ceramics have been fabricated by the solid-state reaction method. The impact of Eu³⁺ doping on the structure, photoluminescence, and electrical properties has been studied by XRD, SEM, PL spectra, and LCR meter. X-ray diffraction analysis reveals that the crystal structure of the samples is well matched with the trigonal perovskite, and the optimal temperature of presintering is 880°C. The Eu³⁺-doped BNT ceramics show excellent red fluorescence at 614 nm corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺ under 466 nm excitation and relatively long fluorescence lifetime. The BNT-0.02Eu ceramic density is up to 5.68 g/cm³ and the relative density is up to 94.6% with sintering temperature 1075°C. The piezoelectric constant (d₃₃) of samples has been significantly improved up to 110 pC/N by Eu³⁺ doping. The BNT-0.03Eu ceramic presintered at 880°C and sintered at 1050°C has good dielectric properties and excellent luminescence properties. Eu³⁺-doped BNT ceramics make it potential applications for novel integrated electro-optical and multifunctional devices.     

溶胶-凝胶法制备(Na0.5Bi0.5)TiO3-BaTiO3基无铅压电陶瓷的研究

采用溶胶-凝胶法制备（Na0.5 Bi 0.5）TiO3-BaTiO3超细粉体。研究结果表明，当热处理温度为800℃时能合成出纯的钙钛矿结构的BNBT超细粉体。另外研究发现，与固相法合成的陶瓷样品相比，sol-gel法制备的陶瓷样品的压电常数和机械品质因子有所提高，但其它的电学性能与固相法合成的陶瓷相近，如介电常数、介电损耗等。     

Temperature-stable Na0.5Bi0.5TiO3-based ceramics with favorable low-temperature dielectric and energy storage property

In this work, (1 − x)(0.94Na_0.5Bi_0.5TiO₃–0.06BaTiO₃)–xKTaO₃ (x = 0–0.30) ceramics are developed for dielectric capacitor applications. The introduction of KTaO₃ from x = 0 to 0.30 increases the tolerance factor t from 0.984 to 1.005 and causes the decrease of ferroelectric rhombohedral phase in the ceramics. Besides, a gradual structural change toward a higher symmetry can be detected, accompanied by the obvious domain refinement. In the aspect of electrical property, the strengthened dielectric relaxation leads to the greatly enhanced thermal stability of dielectric response. The decline in T_s from 98 to −96°C causes a significant widening of the low-temperature region with temperature-stable dielectric constant ε_r and low dielectric loss tan δ. The x = 0.30 ceramic shows a high ε_r (25°C) of 1094 with the temperature coefficient of capacitance ≤±15% over −70 to 200°C, which exceeds the X9R standard. Meanwhile, tan δ is less than 0.02 in a wide temperature range of −35 to 300°C. In addition, the ultrafine grain size of 290 nm, large bandgap of 3.22 eV, and high resistance of the x = 0.30 ceramic contribute to its electrical breakdown strength. A linear-like P–E loop with the large discharged energy density W_D ∼ 3.50 J/cm³ and high energy efficiency η ∼ 90.1% is obtained under 28 kV/mm at room temperature. The thermal stability of the energy storage performance is also satisfactory with the variation of W_D less than 15% over −40 to 200°C, and the η is higher than 85%.     

Domain-scale imaging to dispel the clouds over the thermal depolarization of Bi0.5Na0.5TiO3-based relaxor ferroelectrics

Thermal depolarization temperature, T_d, of ferroelectric oxides Bi_0.5Na_0.5TiO₃ (BNT), where dielectric and piezoelectric signals exhibit remarkable changes, is providing rich research contents but is not well understood yet. Herein, on the domain-scale, we give the direct and clear real-space images of thermal depolarization process on BNT-based complex oxides. As disclosed by the piezoresponse force microscopy (PFM), heating above T_d breaks the poling-induced large-sized-oriented domains into smaller sized polar clusters with different orientations, leading to the thermal depolarization phenomenon. Although the poling-induced domain decays above T_d, the broken domains exhibit a rather larger coherence length than that of the incipient labyrinth-like nano-domains. During the heating process, BNT possesses a structural transition from the long-range-correlated R3c (a⁻a⁻a⁻ anti-phase tilting) to the short-range-correlated P4bm (a⁰a⁰c⁺ in-phase tilting) phase, which should be the fundamental driving force for the fluctuations of poling-induced large-sized-oriented domains. We expect these results will further promote the understanding about the origin of T_d in BNT-based relaxor ferroelectrics, and provide an intuitive method for the characterization of the thermodynamic and kinetic process in this kind of materials.     

无铅压电陶瓷材料的研究现状

本文综述了近年来国内外无铅压电陶瓷材料方面的研究进展,重点介绍了钛酸钡基、铋层状结构、钛酸铋钠基、碱金属铌酸盐系以及钨青铜结构无铅压电陶瓷体系的研究现状,并对无铅压电陶瓷的发展作了展望。     

钛酸铋钠钾锂无铅陶瓷的柠檬酸制备技术

以钠、钾、锂的碳酸盐为原料，采用柠檬酸盐-凝胶法制备了Biol5（Na1-x-y，LixKy）0.5TiO3无铅压电陶瓷，研究了影响凝胶合成的各种工艺条件，利用TG-DTA，SEM，XRD，纳米粒度分析等技术分析了凝胶预烧温度及预烧粉体的粒度分布。研究结果表明：柠檬酸与金属离子的物质的量比、溶液浓度、pH是影响前驱液与凝胶形成的主要因素；用柠檬酸盐一凝胶法合成的Bi0.5（Na1-x-y，LixKy）TiO3粉体粒度细小均匀，合成温度低；陶瓷的压电常数d33可达138pC／N，其平面机电耦合系数kp为0．30。     

Achieving excellent energy storage properties of Na0.5Bi0.5TiO3 - based ceramics by using a two-step strategy involving phase and polarization modification

Na_0.5Bi_0.5TiO₃-based ceramic specimens have been extensively investigated as ferroelectric materials. After being doped with CaTiO₃, the resulting Na_0.5Bi_0.5TiO₃-based ceramics exhibit relaxor characteristics, and improved energy storage density and efficiency. Based on these above results, CeO₂ was further employed to modify the polarization of the 0.85Na_0.5Bi_0.5TiO₃-0.15CaTiO₃ matrix ceramic to achieve better energy storage performance. The effective energy storage density was enhanced from 1.93 to 2.53 J/cm³ by using the appropriate doping concentration of CeO₂. Grain refinement effect can effectively enhance the electric-field strength from approximately 190 to 230 kV/cm. In particular, when doped with 2% CeO₂, the energy storage efficiency of the sample was maintained at approximately 90% at 30 °C-150 °C and at approximately 80% in the frequency range of 0.2–200 Hz. This combination has very excellent temperature stability and frequency stability, making it a promising candidate for energy storage applications.