BaCu(B_2O_5)掺杂对0.4CaTiO_3-0.6(Li_(1/2)Nd_(1/2))TiO_3陶瓷烧结和介电性能的影响

研究了烧结助剂BaCu(B2O5)(BCB)对0.4CaTiO3-0.6(Li1/2Nd1/2)TiO3(CLNT)介质陶瓷的烧结特性、相组成、微观形貌及介电性能的影响。结果表明:添加少量的BCB能使CLNT陶瓷的烧结温度从1300℃降低至1050℃。随着BCB添加量的增加,介电常数下降,频率温度系数向负值偏移。添加4wt%BCB的CLNT陶瓷在1050℃烧结2h,获得了最佳的介电性能:εr=96.5,tanδ=0.017,τf=-13.6ppm/℃,满足高介多层片式微波元器件的设计要求。     

Ca1-x（Li1/2Sm1/2）xTiO3体系微波介质陶瓷的低温烧结研究

采用传统陶瓷制备工艺,制备了添加10 wt%NCB(Na2O-CaO-B3O3)复合氧化物的Ca1-x(Li1/2Sm1/2)xTiO3(x=0.700～0.875)(CLST-x)体系陶瓷,研究了添加NCB后CLST-x体系的晶相组成、显微结构、烧结性能及微波介电性能与组成关系.研究结果表明,添加复合氧化物NCB后,CLST-x体系各组成主晶相仍呈斜方钙钛矿结构,没有其它杂相.添加10wt%NCB后,CLST-x体系陶瓷均可在950℃下烧结致密,在此温度下材料具有较佳的微波介电性能,其中CLST-0.875陶瓷在950℃保温5 h烧结后具有良好的微波介电性能:εr=63.6,Qf=1591 GHz,τ f=0 ppm/℃,可满足高介多层微波器件的设计要求.     

ZnO-B2O3玻璃对Li2Zn3Ti4O12-CaTiO3复合陶瓷低温烧结及性能的影响

采用传统固相反应法制备0.94Li₂Zn₃Ti₄O₁₂-0.06CaTiO₃(LZT-CT)复合陶瓷,采用高温熔融法制备ZnO-B₂O₃(ZB)玻璃;以ZB玻璃为烧结助剂,研究了添加不同质量分数(x=0.5%、1.0%、1.5%、2.0%和2.5%)的ZB玻璃对LZT-CT复合陶瓷的烧结特性、物相组成、微观结构以及微波介电性能的影响。结果表明:ZB玻璃能有效地将LZT-CT复合陶瓷的烧结温度从1 175 ℃降低到875 ℃,并促进了LZT-CT复合陶瓷的致密化。当ZB玻璃掺量x≤2.5%时,LZT-CT复合陶瓷中除了LZT、CT相,没有出现其他新相。随着ZB玻璃添加量增加,复合陶瓷的体积密度、介电常数(ε_r)、品质因数(Q×f)均先增加后减小,谐振频率温度系数(τ_f)变化不大,在(-2.25~4.51)×10^-6/℃波动。当ZB玻璃掺量为2.0%时,LZT-CT复合陶瓷在875 ℃烧结2 h,获得最大体积密度(4.22 g/cm³)以及优异的微波介电性能,ε_r=23.9,Q×f=58 595 GHz,τ_f=-0.14×10^-6/℃。     

Ca-B-Si掺杂对Ba（Zn1／3Ta2／3）O3陶瓷介电性能的影响

采用固相烧结法制备了添加烧结助剂Ca–B–Si（CBS）微晶玻璃的Ba（Zn1/3Ta2/3）O3（BZT）陶瓷。研究了CBS添加量对BZT陶瓷烧结温度和微波介电性能的影响。结果表明,CBS起到助溶剂的作用,添加CBS降低了BZT陶瓷的烧结温度,并改善了微波介电性能。添加2%（质量分数）的CBS时,BZT的烧结温度从纯...     

BBS掺杂的Ca0．3（Li1/2Sm1/2）0.7TiO3微波介质陶瓷的中温烧结研究

采用传统电子陶瓷制备工艺,以42BaO-45B2O-13SiO2(BBS)玻璃为烧结助剂,制备了可以中温烧结的Ca0.3(Li1/2Sm1/2)0.7TiO3 微波介质陶瓷,对陶瓷的晶相组成、烧结性能及微波介电性能进行了系统研究.结果表明:通过液相烧结,BBS玻璃能有效降低Ca0.3(Li1/2m1.2)TiO3陶瓷的烧结温度,由1300℃降低至1000℃.XRD结果显示陶瓷主晶相为斜方钙钛矿,没有发现杂相.随着BBS添加量的增大,陶瓷的介电常数,品质因素以及频率温度系数均呈下降趋势,当BBS的添加量为10wt%时,1000℃下保温5h烧结的陶瓷的致密度、体积密度以及介电常数达到最大值,并具有良好的微波介电性能:ετ=62.5,Qf=1019GHz,τf=21.6ppm/℃.     

ZnO-B2O3-SiO2玻璃对Ca[（Li1／3Nb2／3）0.95Zr0.15]O3＋δ微波介电性能的影响陶瓷

研究了ZnO-B2O3-SiO2（ZBS）玻璃对陶瓷的烧结性能及微波介电特性的影响。研究表明ZBS的掺入能有效降低Ca[（Li1／3Nb2／3）0.95Zr0.15]O3＋δ陶瓷体系的烧结温度150-200℃,谐振频率温度系数随ZBS掺入量增加及烧结温度的提高,由负值向正值方向移动。在1000℃,掺入质量分数7wt％的ZBN,陶瓷微波介电性能最佳：εr=31．1,Qf=9550GHz,Tf=-8．9ppm／℃,在960℃烧结4小时,可获得介电性能为：εf=28．6,Qf=641OGHz,Tf=-9．8ppm／℃陶瓷样品。     

ZBL低温助烧Ca_(0.6)La_(0.8/3)TiO_3-Li_(0.5)Nd_(0.5)TiO_3微波介质陶瓷

通过XRD衍射仪、SEM扫描电镜表征掺杂ZnO-B_2O_3-Li_2O_3(ZBL)低软化点玻璃助烧剂的Ca_(0.6)La_(0.8/3)TiO_3-Li_(0.5)Nd_(0.5)TiO_3(CLLNT)陶瓷样品的物相组成及结构,研究ZBL玻璃的掺杂量对CLLNT样品烧结性能及微波介电性能的影响。研究表明:加入助烧剂(ZBL)后,CLLNT陶瓷的烧结温度降低至950℃;添加9 wt%ZBL玻璃的CLLNT陶瓷在950℃烧结3h,能够获得较好的介电性能:ε_r=82,tanδ=0.0026,τ_f=16 ppm/℃(1 MHz)。     

Ca（0.2）（Li（1/2）Sm（1/2））（0.8）TiO3微波介质陶瓷低温烧结研究

以Ca0.2(Li1/2Sm1/2)0.8TiO3(CLST-0.8)为基料,添加质量分数10%的CaO-B2O3-SiO2(CBS)复合氧化物、4%的Li2O-B2O3-SiO2-CaO-Al2O3(LBSCA)玻璃料和0～2%的CuO氧化物为复合烧结助剂,研究了CuO含量的变化对CLST-0.8陶瓷的低温烧结行为及微波介电性能的影响.随着CuO添加量的增加,陶瓷体积密度、介电常数εr、无载品质因数与谐振频率乘积Qf值,都呈先增加后降低,谐振频率温度系数τf则呈先降低后升高的趋势.添加10%CBS、4.0%LBSCA和1.0%CuO的CLST-0.8微波介质陶瓷,可在900℃下保温5h烧结,并具有较佳的微波介电性能:εr=58.36,Qf=2011GHz, τf=3.44 ppm/℃.     

ZnO-B2O3-SiO2玻璃对Ca[(Li1/3Nb2/3)0.95Zr0.15]O3+δ陶瓷微波介电性能的影响

研究了ZnO-B2O3-SiO2(ZBS)玻璃对陶瓷的烧结性能及微波介电特性的影响.研究表明ZBS的掺入能有效降低Ca[(Li1/3Nb2/3)0.95Zr0.15]O3+δ陶瓷体系的烧结温度150-200℃,谐振频率温度系数随ZBs掺入量增加及烧结温度的提高,由负值向正值方向移动.在1000℃,掺入质量分数7wt%的ZBN,陶瓷微波介电性能最佳:εr=31.1,Qf=9530GHz,τf=8.9ppm/℃.在960℃烧结4小时,可获得介电性能为:εг=28.6,Qf=6410GHz,τf=-9.8ppm/℃陶瓷样品.     

B2O3掺杂对α-CaSiO3/Al2O3陶瓷低温烧结及微波介电性能的影响

通过传统固相法制备了α-CaSiO3/Al2O3-B2O3微波介质陶瓷,研究了不同B2 O3添加量对α-CaSiO3/Al2O3陶瓷烧结特性、相组成及微波介电性能的影响,通过XRD、SEM和网络分析仪对其相结构、微观形貌和微波介电性能进行了表征.结果表明:B2 O3的添加使陶瓷的烧结温度从1375℃降低到了1100℃,并使主晶相由α-CaSiO3相变为β-CaSiO3相;当B2 O3的添加量为3wt%时,在1100℃烧结2 h可获得最佳微波介电性能:εr=6.21,Q×f=30471 GHz,τf=-34.58 ppm/℃.     

Broadband dielectric spectroscopy of PbMg1/3Nb2/3O3–PbSc1/2Nb1/2O3 ceramics

Broadband dielectric spectroscopy results of various ordered and disordered (1 ? x)Pb(Mg_1/3Nb_2/3)O₃–(x)Pb(Sc_1/2Nb_1/2)O₃ (PMN–PSN) ceramics are investigated in the temperature range from 80 K to 300 K and frequency range from 20 Hz to 2 THz. Dielectric dispersion is very broad and in the ferroelectrics case (x = 1, 0.95) consists of two parts: low-frequency part caused by ferroelectric domains and higher frequency part caused by soft mode. The relaxational soft mode exhibits pronounced softening close to phase transition temperature, as it is typical for order–disorder phase transitions. By substituting Sc³⁺ by Mg²⁺ in PMN–PSN ceramics relaxation slows down, and for relaxors (x = 0.2) the most probable relaxation frequency decreases on cooling according to Vogel–Fulcher law.     

Ferroelectric Ceramics in the PbMg1/3Nb2/3O3-PbCd1/3Nb2/3O3 System

Solid solutions (1-x)PbMg_1/3Nb_2/3O₃ + xPbCd_1/3Nb_2/3O₃ with x = 0-0.30 are investigated with purpose to work out a capacitor ceramics with good dielectric properties and low sintering temperature. It is found that the perovskite phase forms at sintering near to 980°C and begins to decompose at higher temperatures. When x grows from 0 to 0.30, the Curie temperature linearly grows from -10°C to +25°C, the dielectric permittivity ε_m in the Curie point T_C decreases from 18000 to 6800 and the phase transition becomes more diffused. The dielectric permittivity at room temperature is rather high and the temperature stability is improved. The system is of interest, because it can serve as a base for working out some ceramic materials for capacitors with low sintering temperature, which needs of no special atmosphere at burning.     

Large strain response with low driving field in Bi1/2Na1/2TiO3–Bi1/2K1/2TiO3–Bi(Mg2/3Nb1/3)O3 ceramics

The (1?x)(0.8Bi_1/2Na_1/2TiO₃–0.2Bi_1/2K_1/2TiO₃)?xBiMg_2/3Nb_1/3O₃ (100xBMN) ternary solid solutions were designed and prepared using a conventional solid‐state reaction. Temperature and compositional dependent ferroelectric, piezoelectric, dielectric features, and structural evolution were systematically studied. At the critical composition of 2BMN, a large bipolar strain of 0.43% was achieved at 55 kV/cm, and the normalized strain reaches to 862 pm/V at a low driving electric field of 40 kV/cm. It was found that the substitution of BiMg_2/3Nb_1/3O₃ induces a transformation from ferroelectric to relaxor phase by disrupting the long range ferroelectric order. Therefore, as the external electric field was applied, a relaxor‐ferroelectric phase transition will be induced. This is contributed to the giant strain. The results above suggest that such a ternary composition is a promising candidate for application to actuator.     

Negative thermal expansion of (Al1/3Fe1/3Cr1/3)2(Mo1/2W1/2)3O12 (AFCMW) and low thermal expansion of AFCMW-(Co1/2Ni1/2)(Mo1/2W1/2)O4 with high entropy

A₂Mo₃O₁₂ (A-Al, Fe, Cr) have large negative thermal expansion (NTE) coefficients and structural stability but high phase-transition temperatures (PTTs). Herein, we prepared (Al_1/3Fe_1/3Cr_1/3)₂(Mo_1/2W_1/2)₃O₁₂ (AFCMW), and found it to have a low NTE coefficient and a low PTT. Furthermore, combination of AFCMW with (Co_1/2Ni_1/2)(Mo_1/2W_1/2)O₄ (CNMW) afforded an AFCMW–CNMW composite with a low thermal expansion (LTE). We determined that the PTT reductions in A₂Mo₃O₁₂ are largely due to the high-entropy effect resulting from the introduction of different ions into its A and M sites. Moreover, we found that the low LTE of the AFCMW–CNMW composite is attributable to the opposite thermal expansion behaviours of AFCMW and CNMW. We suggest that the suppressed thermal expansion during the phase transition process of the AFCMW–CNMW composite could be derived from the high-entropy effect resulting from its increased diversity of polyhedra, the influence of Co²⁺ and Ni²⁺ dopants, and CNMW-induced lattice distortion.     

ICP-AES原子发射分析法检测LiNi1/3Co1/3Mn1/3O2中Ni含量

建立了一套可用于实际电池及材料生产、研制的电池材料镍钴锰酸锂中Ni的测定方法。在解决了原子发射法的基体效应及光谱干扰问题后,选定合适的分析条件,进行方法的准确度和精密度实验,数据结果显示方法可以满足实际分析工作的要求。     

MgF2包覆对正极材料LiNi1/3Co1/3Mn1/3O2性能的影响

通过浸渍法在正极材料LiNi1/3Co1/3Mn1/3O2的表面包覆MgF2,通过XRD、SEM、交流阻抗（EIS）分析、充放电测试研究了不同量MgF2包覆对LiNi1/3Co1/3Mn1/3O2正极材料的结构与电化学性能的影响。结果表明,MgF2以非晶态形式包覆于LiNi1/3Co1/3Mn1/3O2材料颗粒的表面,当包覆量为3%（物质的量分数,下同）时,三元正极材料具有优良的电化学性能,在3.0~4.6 V充放电范围内0.1C充放电倍率下,首次放电比容量为196.3 mA·h/g,1C循环50次后容量保持率为95.7%,55 ℃高温下1C循环50次后容量保持率为93.3%。     

Electromechanical properties of Mn-doped Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 piezoelectric ceramics

The dielectric, piezoelectric, and ferroelectric properties of Mn-doped and undoped yPb(In_1/2Nb_1/2)O₃-(1−x−y)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PIN-PMN-PT) ternary ceramics with morphotropic phase boundary composition have been investigated. Mn-doped PIN-PMN-PT ceramics show obvious hardening characteristics. With 2 mol% Mn doping the mechanical quality factor Q_m can be increased to as high as 2000, while the electromechanical coupling factor (k_p=57%) is still comparable to that of the undoped counterpart. The internal bias field E_i was analyzed and calculated based on the P-E hysteresis loops for the Mn-doped PIN-PMN-PT ceramic. The relatively high Curie temperature, very high Q_m, and low dielectric loss make the Mn-doped PIN-PMN-PT ceramics good candidates for high power and high temperature electromechanical device applications.     

Electrical properties and temperature stability of SrTiO3-modified (Bi1/2Na1/2)TiO3-BaTiO3-(K1/2Na1/2)NbO3 piezoceramics

SrTiO₃-modified lead-free piezoelectric ceramics, (0.93-x)Bi_0.5Na_0.5TiO₃-xSrTiO₃-0.06BaTiO₃-0.01 K_0.5Na_0.5NbO₃ [(BNT-xST)-BT-KNN, x = 0-0.06], were prepared using a conventional solid-state reaction method. The XRD structure analysis and electric properties characteristics revealed the ST-induced phase transformation from the ferroelectric phase to the relaxor phase and their coexistence state. Benefiting from the ST-destructed ferroelectric long-range orders, the high normalized strain value of 600 pm/V was obtained in the (BNT-0.02ST)-BT-KNN ceramic at 5 kV/mm. The ST-generated relaxor phase was found to have a constructive effect on improving the temperature stability and restraining the hysteresis of the electric-field-induced strain. The normalized strain of (BNT-0.06ST)-BT-KNN ceramics could be kept at a high value ~337 pm/V at elevated temperature up to 120°C.     

Macroscopic and Nanoscopic Polarization Relaxation Kinetics in Lead‐Free Relaxors Bi1/2Na1/2TiO3–Bi1/2K1/2TiO3–BiZn1/2Ti1/2O3

The stability of the field‐induced ferroelectric (FE) state was studied in relaxor lead‐free ceramics (1 ? y)[0.81Bi_1/2Na_1/2TiO₃–0.19Bi_1/2K_1/2TiO₃]–yBiZn_1/2Ti_1/2O₃ both macroscopically and microscopically. A strong dc electric field results in the formation of a stable FE state with a large piezoelectric coefficient for compositions with a small amount of Bi(Zn_1/2Ti_1/2)O₃, which are in the non‐ergodic relaxor state at room temperature. Increasing temperature promotes ergodic relaxor behavior, which is accompanied by the rapid destabilization of the induced state, that is, small relaxation times. Based on the obtained data, it is proposed that the depolarization is a two‐step process consisting of an initial realignment of the FE domains and their subsequent breakup into polar nanoregions. The ergodic relaxor behavior is also promoted by increasing the Bi(Zn_1/2Ti_1/2)O₃ content. The related charge disorder results in an enhancement of random electric fields and consequently a stable FE state cannot be induced even at room temperature.     

ZnO-activated formation of phase pure perovskite Pb(In1/2Nb1/2)O3-Pb(Zn1/3Nb2/3)O3-PbTiO3 powder

This paper reports on the phase formation of perovskite Pb(In_1/2Nb_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PZN-PT) powder when doped with 0.04 to 0.83 mol% ZnO. Air calcination of undoped powder mixtures for 4 hours at 800°C resulted in a mixture of Pb₂Zn_0.29Nb_1.71O_6.565 pyrochlore, PIN-PZN-PT perovskite, and In₂O₃. ZnO dopant concentrations as low as 0.04 mol% increased the rate of perovskite formation and resulted in near phase pure perovskite powder of 0.5 μm particle size when heated at 800°C in air. In all cases PbTiO₃ and Pb(In_1/2Nb_1/2)O₃ formed prior to PIN-PZN-PT formation. ZnO doping promotes perovskite phase formation by increasing the reactivity of the intermediate pyrochlore phase by substituting Zn²⁺ on Nb⁵⁺ sites and forming oxygen vacancies when heated in air. Heating in high resulted in an incomplete reaction and a mixture of perovskite and pyrochlore whereas low resulted in phase separation into a mixture of rhombohedral perovskite, tetragonal perovskite, and pyrochlore. The sensitivity clearly shows that oxygen vacancies due to ZnO-doping are critical for synthesis of phase pure PIN-PZN-PT powder.