Bi(Al0.5Sc0.5)O3增强BaTiO3陶瓷弛豫铁电及储能性能EI北大核心CSCD

设计并合成了一种无铅改性BaTiO3基储能陶瓷,通过固相反应法制备了无铅单相钙钛矿BaTiO3–Bi(Al0.5Sc0.5)O3陶瓷,研究了掺杂不同含量BAS对陶瓷的结构、介电性能、铁电性能及储能特性的影响。结果表明:(1–x)BT–x BAS固溶体从四方相(x≤0.05)转变为部分立方相(x≥0.1),但仍以四方相为主且细晶化;随着其含量的增加,Curie温度(Tm)向低温方向移动并出现了介电峰宽化,表现出明显的介电色散行为;BAS的引入破坏了BT陶瓷铁电畴的长程有序,发生了铁电相到弛豫铁电相的相变;2种现象均表明BT–BAS陶瓷具有弛豫铁电体的优异特点。在所有样品中,0.85BT–0.15BAS陶瓷的介电温度稳定性最佳,弛豫因子γ为1.97;外加电场~105 k V/cm时,储能密度为0.684 J·cm–3,储能效率为95.0%,陶瓷具有最佳储能特性。     

Bi(Al_(0.5)Sc_(0.5))O_3增强BaTiO_3陶瓷弛豫铁电及储能性能

设计并合成了一种无铅改性BaTiO_3基储能陶瓷,通过固相反应法制备了无铅单相钙钛矿BaTiO_3–Bi(Al_(0.5)Sc_(0.5))O_3陶瓷,研究了掺杂不同含量BAS对陶瓷的结构、介电性能、铁电性能及储能特性的影响。结果表明:(1–x)BT–x BAS固溶体从四方相(x≤0.05)转变为部分立方相(x≥0.1),但仍以四方相为主且细晶化;随着其含量的增加,Curie温度(T_m)向低温方向移动并出现了介电峰宽化,表现出明显的介电色散行为;BAS的引入破坏了BT陶瓷铁电畴的长程有序,发生了铁电相到弛豫铁电相的相变;2种现象均表明BT–BAS陶瓷具有弛豫铁电体的优异特点。在所有样品中,0.85BT–0.15BAS陶瓷的介电温度稳定性最佳,弛豫因子γ为1.97;外加电场～105 k V/cm时,储能密度为0.684 J·cm~(–3),储能效率为95.0%,陶瓷具有最佳储能特性。     

(1-x)Na0.5 Bi0.5 TiO3-xNaNbO3系无铅压电陶瓷的机电性能

采用传统陶瓷的制备方法,制备了(1-x)Na0.5Bi0.5TiO3-xNaNbO3(r=0～0．08)压电陶瓷。X射线衍射分析表明：所研究的组成均能够形成纯钙钛矿(ABOx)型固溶体。不同频率下陶瓷材料的介电常数-温度曲线显示该体系材料具有典型的弛豫铁电体特征,且随着x的增加,其弛豫性特征愈明显。室温下陶瓷材料的饱和电滞回线表明：所研究组成均为铁电体．材料的剩余极化强度P1在x=0．02时具有最大值。检测了不同组成陶瓷的雎电性能,发现材料的压电常数d33和平面机电耦合系数Kp随着x值的增加先增加后降低,在x=0．02时．陶瓷的d33=88pC／N,Kp=0．1792,为所研究组成中的最大值．材料的介电常数εI3/ε0和介电损耗tanδ则随x值的增加而增加。     

Y_2O_3,Fe_2O_3掺杂(Na_(0.5)Bi_(0.5))TiO_3无铅压电陶瓷的研究

采用固相法制备了(Na0.5Bi0.5)TiO3+xmol%Y2O3+xmol%Fe2O3(0≤x≤1.25)(简称NBTYF)无铅压电陶瓷。XRD衍射结果表明,所有陶瓷样品均为单一的钙钛矿结构。SEM表明,掺杂后陶瓷的晶粒尺寸增大。介电温谱表明该体系陶瓷具有弛豫特性,随掺杂量的增加,退极化温度Td向低温方向移动,而居里温度Tc向高温方向移动。陶瓷的密度和压电常数d33和随x的增加先增大后减小,而机械品质因子Qm一直下降。当x=1.00时,该体系陶瓷具有最佳压电性能,d33=106pC/N,Qm=93,kp=16.08%,εr=594,tanδ=5.33%,ρ=5.699g/cm3。     

Na0.5Bi0.5TiO3-Ba0.5Sr0.5Nb2O6无铅压电陶瓷的研究

采用固相法制备了(1-x)(Na0.5Bi0.5)TiO3-xBa0.5Sr0.5Nb2O6(0≤x≤1.0％)(简称(1-x)NBT-xBSN)无铅压电陶瓷,研究了不同BSN含量(x=0,0.1％,0.3％,0.5％,0.7％,1.0％,摩尔分数)样品的物相组成、显微结构及电性能.结果表明:所有样品均为纯钙钛矿结构,随掺杂量x的增加,陶瓷的相对密度pr、压电常数d33和机电耦合系数kp均先增大后降低,机械品质因子Qm和退极化温度Td则逐渐下降.该体系陶瓷具有弥散相变特征,弥散指数介于1.6～1.7.当x=0.5％时,陶瓷获得最佳性能:d33=92pC/N,kp=0.164,Qm=89,εr=650,tanδ=5.47％,pr=96.5％.     

含Sr铋基焦绿石材料的介电弛豫性能

采用传统固相反应烧结工艺制备(Bi1.5Zn0.5–xSrx)(Ti1.5Nb0.5)O7(BZTN,x=0.30,0.32,0.34,0.36,摩尔分数)铋基焦绿石陶瓷,研究该体系陶瓷的化学组成对物相结构、介电性能和弛豫特性的影响。X射线衍射分析表明:当Sr离子取代量较小时(x0.36),材料的相结构仍然保持立方焦绿石单相结构;当x=0.36时,出现微量SrTiO3杂相,但仍保持立方焦绿石主晶相结构。Sr离子的取代对介电性能产生显著影响:随着Sr离子取代量增加,样品的相对介电常数先增大后减小,介电损耗逐渐减小,并具有较大的正温度系数。观察到铋基焦绿石介电陶瓷的高温介电异常行为:系列样品在200～300℃,均出现明显的介电弛豫现象,并分析与讨论高温介电弛豫性能。     

(Na1-xKx)0.5Bi0.5TiO3系无铅压电陶瓷的电学性能研究

利用固相法制备了(Na1-xKx)0.5Bi0.5TiO3系压电陶瓷,所得陶瓷样品介电损耗tanδ最大不超过5%,最好的压电常数d33=153pC/N,平面机电耦合系数kp=0.299,它们分别出现在x=0.22和0.20处。同时通过对其介电性能的测试,表明该样品具有弛豫铁电性,是典型的弛豫铁电体。     

(Bi_(0.5)Na_(0.5))TiO_3-BaTiO_3系陶瓷的介电弛豫性能

采用传统压电陶瓷固相合成法制得了纯钙钛矿相的( 1 -x) (Bi0 5Na0 5 )TiO3 -xBaTiO3 (x=0 02, 0 04,0 06, 0 08, 0 10) (简写作BNBT)系无铅压电陶瓷。研究了1kHz条件下室温到400℃的温度范围内BNBT试样的介电温谱以及3种不同频率下(1、10、100kHz)BNBT-6试样的介电温谱,发现材料在研究组成范围内均为弛豫型铁电体。采用HRTEM研究了该系统的畴结构,表明BNBT钙钛矿结构铁电体的介电性能与复合离子的有序无序排列密切相关,纳米尺度有序微畴对介电弛豫起着重要作用。     

Phase Transition Behavior and Electrical Properties of （1-x）K（0.5）Na（0.5）NbO3-xCa（0.3）Ba（0.7）TiO3 Lead-Free Piezoelectric Ceramics

采用固相法制备了（1–x）K0.5Na0.5NbO3–xCa0.3Ba0.7TiO3[（1–x）KNN–xCBT]系列无铅压电陶瓷,研究了CBT的含量（x=0～0.08）对样品的物相结构、显微形貌、介电性能以及压电性能的影响。结果表明：所有样品都具有钙钛矿结构;随着x的增加,室温下样品从正交相逐渐向四方相过渡并且Curie温度向低温方向移动,样品的压电常数d33与机电耦合系数kp均先升高后降低。（1–x）KNN–xCBT多晶型转变位于0.03≤x≤0.04,当x=0.03时,样品的压电性能达到最佳：d33=142 pC/N,kp=40%,其介电损耗tanδ从室温到380℃范围内几乎不变且小于0.05,表明组分为x=0.03的陶瓷是一种非常有前景的无铅压电材料。     

W6+掺杂对Na0.5Bi2.5Ta2O9陶瓷的结构与电学性能影响

采用传统固相法制备Na0.5Bi2.5Ta2-xWxO9 (NBTO-x,0≤x≤0.05)无铅压电陶瓷,研究W6+掺杂对NBTO陶瓷结构和电学性能的影响.XRD结果显示,所有陶瓷样品均生成了m=2的铋层状结构化合物,随着掺杂量的增加,样品的正交畸变先减小后增大;W6+掺杂提高了样品的压电与铁电性能,当x=0.03时,...     

Growth and electrical properties of Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 lead-free single crystals by the TSSG method

A series of NBT-KBT lead-free crystals with dimensions of Φ 35×10 mm were successfully grown by the TSSG method. The as-grown crystals possess rhombohedral perovskite structure at room temperature. The curves ε(T) for all crystals show two abnormal dielectric peaks. The depolarization temperatures T_d derived from the first peak of curves tan δ(T) vary with the KBT content, which are 130, 150, 140, and 115 °C respectively, for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals, being well consistent with the T_d obtained from the temperature dependence of k_t. A notable thermal hysteresis, ΔT≈35 °C, for ferroelectric-antiferroelectric phase transition was also disclosed for 92NBT-8KBT crystal. The investigation of orientation dependence for electrical properties disclosed the dielectric parameters show weak anisotropy. The piezoelectric constants (d₃₃) are 147, 175, 205, 238 pC/N and the values of k_t are 38%, 52%, 52%, 54%, respectively for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals.     

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.     

CeO2掺杂钛酸铋钠钾陶瓷的制备工艺与介电性能

为了进一步探索合成工艺对钛酸铋钠系无铅材料的结构及介电特性的影响,本文以甘氨酸为燃料,利用固相-燃烧法制备了CeO2掺杂的Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 (BNKT)陶瓷.XRD表明,在固相合成工艺中引入燃烧法制备BNKT陶瓷,比传统固相法降低预烧温度150 ℃,掺杂的CeO2扩散进入了BNKT钙钛矿的晶格,且当掺杂量为0%~0.3%时,形成纯的钙钛矿相结构;SEM表明,CeO2掺杂使晶粒尺寸趋于平均,对晶粒生长有抑制作用;介电温谱表明,随着CeO2掺杂量增加,介电常数εr和退极化温度Td、相转变温度Tm降低,介电反常峰逐渐弱化,且室温至300 ℃,介电损耗tanδ始终在0.3%以下,并从微结构缺陷空位形成机制角度,结合铁电畴壁运动状态,分析讨论了对材料介电特性的作用规律.     

Bi(Mg0.5Ti0.5)O3 addition induced high recoverable energy-storage density and excellent electrical properties in lead-free Na0.5Bi0.5TiO3-based thick films

(1-x)Na_0.5Bi_0.5TiO₃-xBi(Mg_0.5Ti_0.5)O₃ (NBT-BMT) thick films were designed for achieving large recoverable energy-storage density (W_rec). A large W_rec of 40.4 J/cm³ was detected in the thick film for x = 0.4, which was more than 4 times larger than that of the pure NBT film. The addition of BMT induced slim polarization hysteresis (P-E) loops at room temperature. The slim P-E loops improved the difference between the maximum polarization (P_max) and the remnant polarization (P_r). Besides, a breakdown strength field (BDS) of 2440 kV/cm was also detected in the thick film for x = 0.4. The high BDS was caused by the reduced leakage current density. Furthermore, the thick film for x = 0.4 possessed superior energy-storage stability under different temperature, frequency and electric-field cycling. In addition, 90% of the pulsed discharge energy density could be released in less than 1100 ns by using a pulsed discharge measurement.     

离子对(Nb5+-Cr3+)掺杂对0.93Bi0.5Na0.5TiO3-0.07BaTiO3陶瓷微观结构和电学性能的影响

采用固相烧结法制备(Bi_0.5Na_0.5)_0.93Ba_0.07Ti_1-x(Nb_0.5Cr_0.5)_xO₃(摩尔分数x=0%、0.5%、1%、2%、2.5%、5%)(简称BNBT-xNC)无铅压电陶瓷,研究离子对(Nb⁵⁺-Cr³⁺)对0.93Bi_0.5Na_0.5TiO₃-0.07BaTiO₃(简称BNT-7BT)陶瓷微观结构、介电、铁电和应变性能的影响。结果表明,所有组分为伪立方相。随着离子对(Nb⁵⁺-Cr³⁺)含量增加,BNBT-xNC陶瓷的铁电弛豫特性明显改变,在较低掺杂浓度下(0%≤x≤1%)为非遍历弛豫态,随含量增加(1%≤x≤2%),出现非遍历-遍历弛豫态共存,最后转变为遍历弛豫态(2.5%≤x≤5%);陶瓷从铁电态向弛豫态转变,应变性能先增加后降低,最大应变S_max和逆压电常数d^*₃₃在x=2%时达到最大,分别为0.22%和431 pm/V。     

High permittivitty (La0.5Sr0.5)CoO3-δ-La(Co0.5Ti0.5)O3-δ ceramic composites for next generation MIM capacitors

Dielectrics with low capacitance loss and high relative permittivity are of high demand in metal-insulator-metal (MIM) capacitor that offers higher level of miniaturization, flexibility and performance. In order to achieve high relative permittivity, developing ceramics with metallic inclusions, has been suggested as a working strategy. But such materials may have high leakage currents and often lack thermal stability. With the objective for MIM applications, a series of (1-x)La(Co_0.5Ti_0.5)O_3-δ-x(La_0.5Sr_0.5)CoO_3-δ ceramics [x?=?0.0, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 1] were developed. The crystal structure analysis was performed for La(Co_0.5Ti_0.5)O_3-δ, (La_0.5Sr_0.5)CoO_3-δ and 0.5La(Co_0.5Ti_0.5)O_3-δ-0.5(La_0.5Sr_0.5)CoO_3-δ using X-pert High Score Plus. The composite with x?=?0.5 in (1-x)La(Co_0.5Ti_0.5)O_3-δ-x(La_0.5Sr_0.5)CoO₃-_δ showed a maximum relative permittivity of 4920 with promising ac electrical resistivity (～202?Ω-cm). The thermal, electrical and dielectric properties together suggest that the composition 0.5La(Co_0.5Ti_0.5)O_3-δ-0.5(La_0.5Sr_0.5)CoO₃-_δ is suitable for MIM capacitors in DRAM and RF devices.     

Tuning the electrocaloric effect in 0.94Bi0.5Na0.5TiO3-0.06BaTiO3 ceramics by relaxor phase blending

The pseudo-first-order phase transition in 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ ceramics leads to a sharp increase in temperature change (ΔT) in the vicinity of the ferroelectric-to-relaxor transition temperature T_FR (~100 °C) [Appl. Phys. Lett. 110 (2017) 182904]. In this study, we add the 0.78Bi_0.5Na_0.5TiO₃-0.06BaTiO₃-0.16(Sr_0.7Bi_0.2)TiO₃ relaxor phase to the 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ ferroelectric matrix to tune its electrocaloric effect. The results show that the addition of the relaxor phase plays a vital role in phase and local-structure evolution. A transition occurs between the ferroelectric and ergodic relaxor phases when the mass fraction of the latter increases to 30% (x = 0.3), as verified by X-ray diffraction analysis, Raman spectroscopy, and polarization-electric field (P-E) hysteresis loops. Furthermore, addition of the relaxor phase reduces the T_FR from 76 °C at x = 0.1–55 °C at x = 0.2; however, this transition disappears at x = 0.3 and 0.4 composite. In-situ piezo-force microscopy (PFM) images illustrate that domains can be written into x = 0.1 and 0.2 ceramics with a valley in the piezoresponse curves. Increasing the temperature agitates the domain arrangement and decreases the contrast for PFM images; this indicates a gradual phase transition in the composite. The temperature corresponding to maximum ΔT exhibits a downward shift (0.58 K at 80 °C for x = 0.1 and 0.5 K at 65 °C for x = 0.2), while the temperature-ΔT curves are flat when x = 0.3 and 0.4. Moreover, the maximum ΔT shows a decrease with an increase in the relaxor phase content; this is believed to be related to a decrease in the latent heat due to a pseudo-first-order to second-order transition. Thus, we suggest that the incorporation of a relaxor phase into ferroelectric matrices is an effective technique to tune their electrocaloric effect and improve the thermal stability of ceramic composites.     

Poling effect on optical and dielectric properties of Pr3+-doped Na0.5Bi0.5TiO3 ferroelectric single crystal

In recent years, with increased environmental awareness, more and more research has been carried out for lead-free ferroelectric materials. Among such materials, Na_0.5Bi_0.5TiO₃ (NBT) single crystal has become a material of interest due to its high Curie temperature. In this study, Pr-doped NBT crystals were prepared and poled along different crystal orientations. The effects of different crystal orientations and poling on the optical properties of Pr-doped NBT crystals were investigated. The optical transmission of the crystal decreases after poling along the [001] orientation and increases after poling along the [111] orientation. The emission and excitation spectra show that the poled process enhances the crystal luminescence. The dielectric constant dependence on temperature for different crystal orientations was measured. The domain structure was measured to explain the changes in the optical properties. The optical properties of a Pr-doped NBT single crystal were modulated by poling along different crystal orientations, which is expected to improve the performance of optoelectronic devices based on such materials.     

Enhanced dielectric and energy-storage properties in ZnO-doped 0.9(0.94Na0.5Bi0.5TiO3−0.06BaTiO3)−0.1NaNbO3 ceramics

[0.9(0.94Na_0.5Bi_0.5TiO₃?0.06BaTiO₃)?0.1NaNbO₃]-xZnO (NBT-BT-NN-xZnO, x=0, 0.5 wt%, 1.0 wt%, 1.5 wt%, and 2.0 wt%) ferroelectric ceramics were fabricated using a conventional solid-state reaction method. The effects of ZnO content on dielectric, energy-storage and discharge properties were systematically investigated. Dielectric constant and difference between maximum and remanent polarization were significantly improved by ZnO doping. Dielectric constant of NBT-BT-NN-1.0-wt% ZnO was 3218 at 1 kHz and room temperature, i.e. one time bigger than that of pure NBT-BT-NN ceramic. As a consequence, a maximum energy-storage density of 1.27 J/cm³ with a corresponding efficiency of 67% was obtained in NBT-BT-NN-1.0-wt% ZnO ceramic. Moreover, its pulsed discharge energy density was 1.17 J/cm³, and 90% of which could be released in less than 300 ns. Therefore, ZnO doped NBT-BT-NN ceramic with a large energy-storage density and short release time could be a potential candidate for applications in high energy-storage capacitors.     

The microstructure,ferroelectric and dielectric behaviors of BiFeO3-Na0.5Bi0.5TiO3 based solid solution thin films

BiFe_0.98Zn_0.02O₃-Na_0.5Bi_0.5Ti_0.98W_0.02O₃ solid solution thin films with two thicknesses (300 nm and 1.2 μm) were fabricated on indium tin oxide/glass substrates via metal organic decomposition. The effects of the thickness on crystallization, microstructure morphology, ferroelectric and dielectric properties were investigated. Compared with the 300-nm-thick film, 1.2 μm- film exhibits standard ferroelectric hysteresis loop with slim feature and larger dielectric constant due to the improvements of crystallinity and insulating property. Moreover, obvious aging behavior, manifested by pinched-like ferroelectric hysteresis loop and abnormal butterfly dielectric constant-electric field curve, can be observed in the film with 1.2 μm thickness. The aging behavior can be explained by the formation of the defect complex.