Li2Zn3(1-x)Ca3xTi4O12微波陶瓷介电性能研究

本文以Li2CO3,ZnO,CaCO3,TiO2为原料,采用固相反应法制备了Li2Zn3(1-x)Ca3xTi4O12(x=0,0.05,0.1,0.15)陶瓷,并研究了CaTiO3固溶量对其显微结构和微波介电性能的影响.结果表明:Li2Zn3Ti4O12晶相中固溶CaTiO3相,晶胞参数会增大;少量CaTiO3相固溶于Li2Zn3Ti4O12陶瓷后,提高了Li2Zn3Ti4012陶瓷的烧结温度及其介电常数,但降低了其品质因素,可增大其温频系数.在1100℃/2 h烧结条件下,Li2Zn2.7Ca0.3Ti4O12陶瓷微波介电性能达到:εr=24,Q×f=50000 GHz,Tf=-25×10-6/℃.     

0.6Mg4Nb2O9-0.4SrTiO3复相陶瓷中温烧结和微波介电性能

采用传统固相反应法制备了0.6Mg4Nb2O9-0.4SrTiO3复合陶瓷.研究了LiF掺杂对其烧结特性、显微组织和微波介电性能的影响.实验结果表明:通过添加一定量的LiF,可将Mg4Nb2O9/SrTiO3陶瓷的致密化烧结温度降至1100 ℃;其中掺杂1.5wt% LiF、 1100 ℃下烧结5 h的0.6Mg4Nb2O9-0.4SrTiO3陶瓷微波介电性能为:ε=20.6,Q·f=4057 GHz; 样品的微波介电性能与杂相Sr(Ti1-xNbx)O3+δ和残留液相有关.     

(1-x)Ba4Sm9.33Ti18O54-xCa0.61Nd0.26TiO3系微波介质陶瓷

采用固相合成法制备了(1-x)Ba4Sm9.33Ti18O54-xCa0.61Nd0.26TiO3[(1-x)BST-xCNT]系微波介质陶瓷.探讨了组成、烧结温度对微波介质陶瓷结构、介电性能的影响.x＜0.6时,(1-x)BST-xCNT陶瓷为正交结构的新型钨青铜单相.x≥0.6时,相继出现了第二相Sm2Ti2O7和钙钛矿相,最终形成钙钛矿单相.微波介质陶瓷的介电常数ε随x的增大持续升高,品质因子Qf值则先增大后迅速减小再急剧增大.1 325～1 350 ℃烧结样品的微波介电性能达到最佳:x=0时,ε=75,Qf=8985GHz,谐振频率温度系数τf=-8.2×10-6/℃;x=0.2时,ε=75,Qf=9 552GHz,τf=-14.4×10-6/℃;x=1时,ε=108.9,Qf=14919GHz,τf=236.2×10-6/℃.     

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/℃.     

Zn2+掺杂对0.965MgTiO3-0.035SrTiO3微波介质陶瓷结构与性能影响研究

采用固相反应法制备了0.965 MgTiO3-0.035SrTiO3 (MST)微波介质陶瓷,选用Zn2+对MST陶瓷进行了A位离子掺杂,研究了不同Zn2+掺杂量对陶瓷烧结性能、晶相组成、显微结构及微波介电性能的影响.结果表明,Zn2的掺入促进了陶瓷的烧结,显著提高了陶瓷的致密度,且没有改变陶瓷的主晶相.在掺杂量小于0.04mol％范围内,随着Zn2+掺杂量的增加,陶瓷的介电常数增加,品质因素和频率温度系数略有降低.中间相MgTi2 O5的衍射峰强度随着Zn2+掺杂量的增加逐渐减弱直至完全消失.当Zn2掺杂量为x=0.03时,陶瓷的烧结温度由1380℃降低至1290℃,并呈现优异的微波介电性能:εr=22.51,Q×f=16689 GHz,τf=-4.52×10-6/℃.     

BaCu(B_2O_5)助烧对0.95MgTiO_3-0.05CaTiO_3微波介质陶瓷性能的影响

研究了BaCu(B2O5)的掺入对0.95MgTiO3-0.05CaTiO3微波介质陶瓷介电性能的影响。用XRD和SEM分析其相组成及微观形貌。结果表明:BaCu(B2O5)的加入能够使0.95MgTiO3-0.05CaTiO3陶瓷的烧结温度降至1100℃并有效抑制第二相MgTi2O5的形成。在1100℃烧结3h,加入3wt%BaCu(B2O5)的0.95MgTiO3-0.05CaTiO3陶瓷获得了较好的介电性能:εr=22.9,Q×f=25,000GHz(7GHz),τf=-3.3ppm/℃(7GHz)。     

B2O3-CuO掺杂CSLST微波介质陶瓷介电性能研究

选用B2O3-CuO(BC)低熔点复合氧化物作为烧结助剂,采用固相法制备(Ca0.9375Sr0.0625)0.25(Li0.5Sm0.5)0.75TiO3(CSLST)陶瓷,研究了不同含量的BC对CSLST陶瓷的晶相组成、烧结性能及微波介电性能的影响.研究结果表明:随BC添加量的增多,CSLST陶瓷的烧结温度降低,陶瓷的微波介电常数εr和谐振频率温度系数(Τ)f下降,品质因素Qf明显降低.当BC添加量为5wt％时,在1000℃保温5h可烧结,此时陶瓷具有较佳的微波介电性能:εr=80.4,Q×f=1380 GHz,(Τ)f=- 32.89×10-6/℃.     

Mg4Nb2O9/CaTiO3复合介质陶瓷的结构和介电性能

以1.7%(质量分数)V2O5为烧结助剂,采用传统固相反应法制备了(1-x)Mg4Nb2O9 xCaTiO3[(1-x)MN-xCT]颗粒复合微波介质陶瓷.研究了陶瓷的微观结构和微波介电性能.结果表明:当0.5≤x≤0.7时,经1 150℃烧结5 h制备的(1-x)MN-xCT样品仍为Mg4Nb2O9和CaTiO3相,没有生成其它新相,在不同相之间存在元素扩散.当x从0.3增加到0.7,样品的相对介电常数(εr)和谐振频率(f)温度系数(τf)随x值的增加而增大,而品质因数(Q)却随x增大而降低.当x=0.5,1 150℃烧结5h后,获得的0.5Mg4Nb2O9/0.5CaTiO3 1.7%V2O5微波介质陶瓷的εr=20,Qf=48000 GHz(f=8 GHz),τf=12×10-6/℃.     

0.7CaTiO3-0.3Sm1-xAlO3陶瓷微波介电性能研究

采用固相反应法制备了0.7CaTiO3-0.3Sm1-xAlO3(CTSA,0≤x≤0.1)微波介质陶瓷,研究了Sm缺位对CTSA陶瓷的晶体结构、微观形貌以及微波介电性能的影响。结果表明,制备的CTSA陶瓷均为正交钙钛矿结构。少量的Sm缺位能够降低CTSA陶瓷的烧结温度,晶粒尺寸增加,同时气孔率增大,陶瓷的Q×f值也有显著提升。当x=0.025、烧结温度为1450℃时,CTSA陶瓷具有最佳微波介电性能:εr=45.2,Q×f=47280GHz和τf=+4.8 ppm/℃。     

(Mg1-xCox)TiO3基微波陶瓷介电性能研究

以MgO,Co2O3和TiO2为原料,用固相反应法制备了(Mg1-xCox)TiO3(MCT)系陶瓷.研究了CoTiO3含量对其微观结构和微波介电性能的影响.结果表明:添加适量的CoTiO3,可以适当降低烧结温度,调整烧结温度范围.当掺入量为10 mol%,烧结温度为1350 ℃时,MCT陶瓷具有优良微波介电性能:εr=18.99;Q×f=154000 GHz,τf=-45 ppm/℃.     

Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3–SrTiO3陶瓷的准同型相界与电性能

采用固相法制备了 Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3–BaTiO3–SrTiO3（NBT–KBT–BT–ST）陶瓷,该体系是按（1–2x）（0.8NBT–0.2KBT）–x（0.94NBT–0.06BT）–x（0.74NBT–0.26ST） （x = 0.10、0.20、0.25、0.30、0.35、0.40、0.45）组合而成的,研究了该系陶瓷的结构与电性能。结果表明：所有样品都处于三方–四方准同型相界区域。该系陶瓷在准同型相界附近表现出了优异的压电性能,压电常数 d33、机电耦合系数 kp和剩余极化强度 Pr随 x 的增加先升高后降低,其中 x=0.35 陶瓷的电性能最佳：d33= 210 pC/N,kp= 0.319,Pr= 39.3 μC/cm2,Ec= 20.2 kV/cm,是一种良好的无铅压电陶瓷候选材料。依据准同型相界组成的线性组合规律来寻找具有优异压电性能的 NBT–KBT–BT–ST 陶瓷准同型相界组成是可行的。     

Sintering of glass-added BaZn1/3Nb2/3O3 ceramics

The complex perovskite oxide Ba(Zn_1/3Nb_2/3)O₃ (BZN) has been studied for its attractive dielectric properties which place this material interesting for applications as multilayer ceramics capacitors or hyperfrequency resonators. This material is sinterable at low temperature with combined glass phase–lithium salt additions, and exhibits, at 1 MHz very low dielectric losses combined with relatively high dielectric constant and a good stability of this later versus temperature. The 2 wt.% of ZnO–SiO₂–B₂O₃ glass phase and 1 wt.% of LiF-added BZN sample sintered at 900 °C exhibits a relative density higher than 95% and attractive dielectric properties: a dielectric constant ?_r of 39, low dielectrics losses (tan(δ) < 10⁻³) and a temperature coefficient of permittivity τ_? of 45 ppm/°C⁻¹. The 2 wt.% ZnO–SiO₂–B₂O₃ glass phase and 1 wt.% of B₂O₃-added BZN sintered at 930 °C exhibits also attractive dielectric properties (?_r = 38, tan(δ) < 10⁻³) and it is more interesting in terms of temperature coefficient of the permittivity (τ_? = −5 ppm/°C). Their good dielectric properties and their compatibility with Ag electrodes, make these ceramics suitable for L.T.C.C applications.     

Graphite trifluoromethylsulfate C12+SO3CF3−

Graphite trifluoromethylsulfate C₁₂SO₃CF₃, a new binary graphite salt is formed by the irreversible solvolysis of C₈SO₃F in a large excess of trifluoromethylsulfuric acid. The salt is identified as a stage one intercalation compound with a C₀ value of 8.12 Å and characterised by microanalysis, epr and ¹⁹F NMR spectroscopy. Both Raman spectra, in the back scattering configuration, and IR spectra, in transmission as well as reflection geometries, are used to support an ionic formulation as C₁₂⁺SO₃CF₃^?.     

Solid state metathesis synthesis of BaTiO3, PbTiO3, K0.5Bi0.5TiO3 and Na0.5Bi0.5TiO3

A solid state metathesis approach has been applied to synthesize perovskite oxides such as BaTiO₃, PbTiO₃, K_0.5Bi_0.5TiO₃ and Na_0.5Bi_0.5TiO₃, these were characterized by powder XRD, IR and energy dispersive spectra (EDS). Potassium titanium oxalate and metal chlorides are used as the starting materials. X-ray analysis shows the formation of a single phase with tetragonal structure for BaTiO₃, PbTiO₃, K_0.5Bi_0.5TiO₃ and a monoclinic structure for Na_0.5Bi_0.5TiO₃. The Infrared spectra of these compounds show the characteristic band due to Ti–O octahedron for all the compounds. The EDS spectra show the relative ratio of the metal ions. The morphology of synthesized compounds was obtained from SEM measurements.     

Al2O3包覆LiNi1/3Co1/3Mn1/3O2锂离子电池正极材料

综述了Al2O3包覆LiNi(1/3)Co(1/3)Mn(1/3)O2锂离子电池正极材料的研究现状与进展,并评述了其制备方法和包覆改性;讨论了包覆改善该正极材料性能的机理;提出了这种正极材料的研发过程中的一些问题并对其未来的发展前景作了展望。     

Fabrication and piezoelectric properties of BaTiO3/BaTiO3-Bi(Mg1/2Ti1/2)O3-BiFeO3 composites

We fabricated xBaTiO₃ (BT)/(1-x)[BaTiO₃-Bi(Mg_1/2Ti_1/2)O₃-BiFeO₃] (BT-BMT-BF)?+?0.1?wt%MnCO₃ composites by spark plasma sintering and investigated the effect of BT content x, BT powder size, and BT-BMT-BF composition on piezoelectric properties. For xBT/(1-x)(0.3BT-0.1BMT-0.6BF) +?0.1?wt%MnCO₃ (x?=?0–0.75) composites with a 0.5-µm BT powder, the dielectric constant was increased with x, and the relative density was decreased at x?=?0.67 and 0.75, creating optimum BT content of x?=?0.50 with a piezoelectric constant d₃₃ of 107?pC/N. When a larger 1.5-µm BT powder was utilized for the composite with x?=?0.50, the d₃₃ value increased to 150?pC/N due to the grain size effect of the BT grains. To compensate for a compositional change from the optimum 0.3BT-0.1BMT-0.6BF due to partial diffusion between the BT and 0.3BT-0.1BMT-0.6BF grains, a 0.5BT/0.5(0.275BT-0.1BMT-0.625BF)?+?0.1?wt%MnCO₃ composite with the 1.5-µm BT powder was fabricated. We obtained an increased d₃₃ value of 166?pC/N. These results provided a useful composite design to enhance the piezoelectric properties.     

Surface of LiCo1/3Ni1/3Mn1/3O2 modified by CeO2-coating

A novel method to improve the cycling performance of LiCo_1/3Ni_1/3Mn_1/3O₂ in lithium-ion batteries by 1.0 wt.% CeO₂-coating is presented in this work. The crystalline structure and morphology of the synthesized powder have been characterized by XRD, SEM, TEM and their electrochemical performances were evaluated by CV, EIS and galvonostatic charge/discharge tests. It is found that CeO₂ forms a layer on the surface of LiCo_1/3Ni_1/3Mn_1/3O₂ without destroying the crystal structure of the core material. Electrochemical test indicates that CeO₂-coating could improve the cycling performance of LiCo_1/3Ni_1/3Mn_1/3O₂. At room temperature, the capacity retention of 1.0 wt.% CeO₂-coated material is 93.2% after 12 cycles at 3.0 C while that of the bare sample is only 86.6%. ICP-OES proves the coating layer could protect the dissolution of the transition metal ions from LiCo_1/3Ni_1/3Mn_1/3O₂. From the analysis of EIS, the improvement of cycle ability could be attributed to the suppression of the reaction between cathode and electrolyte.     

Nb2O5-supported WO3: a comparative study with WO3/Al2O3

WO₃/Nb₂O₅-supported samples prepared by impregnation are characterised by X-ray diffraction (XRD), Raman spectroscopy and X-ray absorption spectroscopy (XAS) at the W–L₃ absorption edge, as well as temperature programmed reduction (TPR) and FT-IR monitoring of pyridine adsorption. Results are compared with those obtained for WO₃/Al₂O₃ samples prepared in the same conditions, showing that niobia is able to disperse tungsta better than alumina does. Formation of a crystalline WO₃ needs larger tungsten contents on niobia than on alumina, since tungsten solution into niobia is easier than into alumina. Raman and XAS spectra recorded under ambient conditions suggest that similar WO_x species are formed on both supports at tungsten contents 0.5–1 theoretical monolayers; however, TPR results for the low tungsten loaded samples indicate that, when reduction starts (always at temperatures higher than 700 K under H₂/Ar flow) there is a larger concentration of tetrahedral [WO₄] species on alumina, than on niobia. Samples with low tungsten loading have been tested in isopropanol decomposition and ethylene oxidation, following both processes by FT-IR of adsorbed species up to 673 K. Results show that adsorption of ethylene on WO₃/Nb₂O₅ yields acetaldehyde and acetate at 473 K, while this adsorption is non-reactive either on the supports or on WO₃/Al₂O₃. Isopropanol adsorbs dissociatively on both supports, leading to acetone and propene formation on tungsta–niobia, but only propene on tungsta–alumina, probably due to the larger reducibility of the tungsten-containing phases.     

Sintering of Si3N4-Y2O3-Al2O3

Sintering kinetics of the system Si₃N4-Y2O₃-Al₂O3 were determined from measurements of the linear shrinkage of pressed disks sintered isothermally at 1500° to 1700°C. Amorphous and crystalline Si₃N₄ were studied with additions of 4 to 17 wt% Y₂O₃ and 4 wt% A1₂O₃. Sintering occurs by a liquid-phase mechanism in which the kinetics exhibit the three stages predicted by Kingery's model. However, the rates during the second stage of the process are higher for all compositions than predicted by the model. X-ray data show the presence of several transient phases which, with sufficient heating, disappear leaving mixtures of β ' -Si₃N₄ and glass or β '-Si₃N₄, α '-Si₃N₄, and glass. The compositions and amounts of the residual glassy phases are estimated.