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1.
Solid solutions of (Ba0.9−xSrxCa0.1)(Ti0.8Zr0.2)O3 (BSCTZ) (0.1≤x≤0.4) were prepared using the conventional solid state reaction method. The effects of the substitution content on the crystallographic structure, phase transition and dielectric properties of the samples were investigated by dielectric and Raman spectroscopy over a wide temperature range from 100 to 500 K. All the samples were noted to undergo a diffuse phase transition from the tetragonal to the cubic phase and to exhibit a relaxor ferroelectric behavior.  相似文献   

2.
This paper reports the synthesis, structure, chemical stability and electrical transport properties of Ti substituted Ba3CaNb2O9 (BCN) to develop electrolytes for proton conducting solid oxide fuel cells (H-SOFCs). The powder X-ray diffraction (PXRD) of Ba3CaNb2−xTixO9−δ (x = 0.1, 0.15, 0.2, 0.25 and 0.3) and Ba3Ca1.18Nb1.82−xTixO9−δ (x = 0.15 and 0.25) showed formation of double perovskite-like structure with lattice constant comparable to that of Ba3Ca1.18Nb1.82O9−δ (BCN18). Scanning electron microscopy (SEM) showed dense and pore-free microstructure for Ba3CaNb1.75Ti0.25O8.875. PXRD and Fourier transform infrared (FTIR) spectroscopy data confirmed long-term stability of Ba3CaNb2−xTixO9−δ and Ba3Ca1.18Nb1.82−xTixO9−δ in boiling H2O and in CO2 at elevated temperatures. The AC impedance investigation showed contribution due to bulk, grain-boundary and electrode effect at low temperatures. The electrical conductivity of studied materials were measured in different medium including dry air, dry H2, wet H2, wet N2 and D2O. Increase in conductivity in wet N2 and decrease in conductivity in D2O confirmed the proton conduction in Ba3CaNb1.75Ti0.25O9-δ. Among Ti-substituted compounds investigated in this study, Ba3Ca1.18Nb1.57Ti0.25O8.605 showed the highest conductivity of 3.5 × 10−4 S cm−1 at 400 °C in wet N2 (3%H2O), which is comparable to reported values of Ba2Ca0.79Nb0.66Ta0.55O6−δ and BCN18.  相似文献   

3.
Br-doped Li4Ti5O12 in the form of Li4Ti5O12−xBrx (0 ≤ x ≤ 0.3) compounds were successfully synthesized via solid state reaction. The structure and electrochemical properties of the spinel Li4Ti5O12−xBrx (0 ≤ x ≤ 0.3) materials were investigated. The Li4Ti5O12−xBrx (x = 0.2) presents the best discharge capacity among all the samples, and shows better reversibility and higher cyclic stability compared with pristine Li4Ti5O12, especially at high current rates. When the discharge rate was 0.5 C, the Li4Ti5O12−xBrx (x = 0.2) sample presented the excellent discharge capacity of 172 mAh g−1, which was very close to its theoretical capacity (175 mAh g−1), while that of the pristine Li4Ti5O12 was 123.2 mAh g−1 only.  相似文献   

4.
Lead-free piezoelectric ceramics Ba0.90Ca0.10Ti1−xSnxO3 have been prepared by a conventional ceramic fabrication technique and the effects of Sn4+ on the structure, dielectric and piezoelectric properties of the ceramics have been investigated. All the ceramics exhibit a pure perovskite structure. After the substitution of Sn4+, the crystal structure of ceramics is transformed gradually from a tetragonal to an orthorhombic phase, and becomes a pseudo-cubic phase at x≥0.14. The substitution also decreases the Curie temperature greatly from 138 °C at x=0 to 33 °C at x=0.12, and shifts the orthorhombic–tetragonal phase transition to higher temperatures. Coexistence of the orthorhombic and tetragonal phases is formed in the ceramic at x=0.10, leading to significant improvements in the piezoelectric properties: d33=521 pC/N and kp=45.5%. Our results also reveal that the ceramics sintered at higher temperatures contain larger grains, and thus exhibit more noticeable tetragonal–orthorhombic phase transition and enhanced ferroelectric and piezoelectric properties.  相似文献   

5.
(1 − x)Ba0.4Sr0.6TiO3/xCaCu3Ti4O12 composite ceramics were prepared by spark plasma sintering. Sintering behavior, microstructures and dielectric properties of the composite ceramics were investigated by XRD, SEM, EDS and dielectric spectrometer. Dense composite ceramics consisting of Ba0.4Sr0.6TiO3 phase and CaCu3Ti4O12 phase were prepared at 800 °C for 0 min. The dielectric loss of the composite ceramic decreased with increasing amount of Ba0.4Sr0.6TiO3, and the high dielectric constant were retained. Moreover, the better temperature stability of dielectric constant was obtained. These improvements of dielectric characteristics have great scientific significance for potential application.  相似文献   

6.
Preparation of the (Ti1−xNbx)2AlC solid solution (formed from the Mn+1AXn or MAX carbides, where n = 1, 2, or 3, M is an early transition metal, A is an A-group element, and X is C) with x = 0.2-0.8 was investigated by self-propagating high-temperature synthesis (SHS). Nearly single-phase (Ti,Nb)2AlC was produced through direct combustion of constituent elements. Due to the decrease of reaction exothermicity, the combustion temperature and reaction front velocity decreased with increasing Nb content of (Ti1−xNbx)2AlC formed from the elemental powder compacts. In addition, the samples composed of Ti, Al, Nb2O5, and Al4C3 were adopted for the in situ formation of Al2O3-added (Ti,Nb)2AlC. The SHS process of the Nb2O5/Al4C3-containing sample involved aluminothermic reduction of Nb2O5, which not only enhanced the reaction exothermicity but also facilitated the evolution of (Ti,Nb)2AlC. Based upon the XRD analysis, two intermediates, TiC and Nb2Al, were detected in the (Ti,Nb)2AlC/Al2O3 composite and their amounts were reduced by increasing the extent of thermite reduction involved in the SHS process. The laminated microstructure characteristic of the MAX carbide was observed for both monolithic and Al2O3-added (Ti,Nb)2AlC solid solutions synthesized in this study.  相似文献   

7.
The La2−xAxMo2O9−δ (A = Ca2+, Sr2+, Ba2+ and K+) series has been synthesised as nanocrystalline materials via a modification of the freeze-drying method. The resulting materials have been characterised by X-ray diffraction (XRD), thermal analysis (TG/DTA, DSC), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The high-temperature β-polymorph is stabilised for dopant content x > 0.01. The nanocrystalline powders were used to obtain dense ceramic materials with optimised microstructure and relative density >95%. The overall conductivity determined by impedance spectroscopy depends on both the ionic radius and dopant content. The conductivity decreases slightly as the dopant content increases in addition a maximum conductivity value was found for Sr2+ substitution, which show an ionic radii slightly higher than La3+ (e.g. 0.08 S cm−1 for La2Mo2O9 and 0.06 S cm−1 for La1.9Sr0.1Mo2O9−δ at 973 K). The creation of extrinsic vacancies upon substitution results in a wider stability range under reducing conditions and prevents amorphisation, although the stability is not enhanced significantly when compared to samples with higher tungsten content. These materials present high thermal expansion coefficients in the range of (13-16) × 10−6 K−1 between room temperature and 753 K and (18-20) × 10−6 K−1 above 823 K. The ionic transport numbers determined by a modified emf method remain above 0.98 under an oxygen partial pressure gradient of O2/air and decreases substantially under wet 5% H2-Ar/air when approaching to the degradation temperature above 973 K due to an increase of the electronic contribution to the overall conductivity.  相似文献   

8.
La(1−x)SrxFeO3 (x = 0.2,0.4) powders were prepared by a stearic acid combustion method, and their phase structure and electrochemical properties were investigated systematically. X-ray diffraction (XRD) analysis shows that La(1−x)SrxFeO3 perovskite-type oxides consist of single-phase orthorhombic structure (x = 0.2) and rhombohedral one (x = 0.4), respectively. The electrochemical test shows that the reaction at La(1−x)SrxFeO3 oxide electrodes are reversible. The discharge capacities of La(1−x)SrxFeO3 oxide electrodes increase as the temperature rises. With the increase of the temperature from 298 K to 333 K, their initial discharge capacity mounts up from 324.4 mA h g−1 to 543.0 mA h g−1 (when x = 0.2) and from 147.0 mA h g−1 to 501.5 mA h g−1 (when x = 0.4) at the current density of 31.25 mA g−1, respectively. After 20 charge-discharge cycles, they still remain perovskite-type structure. Being similar to the relationship between the discharge capacity and the temperature, the electrochemical kinetic analysis indicates that the exchange current density and proton diffusion coefficient of La(1−x)SrxFeO3 oxide electrodes increase with the increase of the temperature. Compared with La0.8Sr0.2FeO3, La0.6Sr0.4FeO3 electrode is a more promising candidate for electrochemical hydrogen storage because of its higher cycle capacity at various temperatures.  相似文献   

9.
Al-doped Li4Ti5O12 in the form of Li4−xAlxTi5O12 (x = 0, 0.05, 0.1 and 0.2) was synthesized via solid state reaction in an Ar-flowing atmosphere. Al-doping does not change the phase composition and particle morphology, but easily results in the lattice distortion and thus the poor crystallinity of Li4Ti5O12. Al-doping decreases the specific capacity of Li4Ti5O12, while improves remarkably its cycling stability at high charge/discharge rate. The substitution of Al for Li site can enhance the electronic conductivity of Li4Ti5O12 via the generation of mixing Ti4+/Ti3+, whereas impede the Li-ion diffusion in the lattice. Excessive Al causes large electrode polarization due to the lower Li-ion conductivity, and thus leads to low specific capacity at high current densities. Li3.9Al0.1Ti5O12 exhibits a relatively high specific capacity and an excellent cycling stability.  相似文献   

10.
(1 − x)Pb(Sn1−yTiy)O3-xPb(Mg1/3Nb2/3)O3 (x = 0.1-0.4, y = 0.45-0.65) ternary system was prepared using two-step columbite precursor method. Phase structure of the synthesized ceramics was studied by using X-ray powder diffraction and the morphotropic phase boundary (MPB) curve of the ternary system was confirmed. The isothermal map of Curie temperature (TC) in the phase diagram was obtained based on the dielectric-temperature measurements. The coercive field EC and internal bias field Ei were found to increase with increasing PT content, while decrease with increasing PMN content. The optimum properties were achieved in the MPB composition 0.8Pb(Sn0.45Ti0.55)O3-0.2Pb(Mg1/3Nb2/3)O3, with dielectric permittivity ?r, piezoelectric coefficient d33, planar electromechanical coupling kp, mechanical quality factor Qm and TC of being on the order of 3040, 530pC/N, 55.5%, 320 and 190 °C, respectively, exhibiting potential usage for high power application.  相似文献   

11.
This study reports the successful preparation of single-phase perovskite (Ba0.5Sr0.5)0.8La0.2Fe1−xMnxO3−δ (x = 0-0.2) by the citrate-EDTA complexing method. The crystal structure, thermal gravity analysis, coefficient of thermal expansion, electrical conductivity, and electrochemical performance of (Ba0.5Sr0.5)0.8La0.2Fe1−xMnxO3−δ were investigated to determine its suitability as a cathode material for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The lattice parameter a of (Ba0.5Sr0.5)0.8La0.2Fe1−xMnxO3−δ decreases as the amount of Mn doping increases. The coefficients of thermal expansion of the samples are in the range of 21.6-25.9 × 10−6 K−1 and show an abnormal expansion at around 400 °C associated with the loss of lattice oxygen. The electrical conductivity of the (Ba0.5Sr0.5)0.8La0.2Fe1−xMnxO3−δ samples decreases as the amount of Mn-doping increases. The electrical conductivity of the samples reaches a maximum value at around 400 °C and then decreases as the temperature increases. The charge transfer resistance, diffusion resistance and total resistance of a (Ba0.5Sr0.5)0.8La0.2Fe0.8Mn0.15O3-δ-Ce0.8Sm0.2O1.9 composite cathode electrode at 800 °C are 0.11 Ω cm2, 0.24 Ω cm2 and 0.35 Ω cm2, respectively.  相似文献   

12.
Li4AlxTi5−xFyO12−y compounds were prepared by a solid-state reaction method. Phase analyses demonstrated that both Al3+ and F ions entered the structure of spinel-type Li4Ti5O12. Charge-discharge cycling results at a constant current density of 0.15 mA cm−2 between the cut-off voltages of 2.5 and 0.5 V showed that the Al3+ and F substitutions improved the first total discharge capacity of Li4Ti5O12. However, Al3+ substitution greatly increased the reversible capacity and cycling stability of Li4Ti5O12 while F substitution decreased its reversible capacity and cycling stability slightly. The electrochemical performance of the Al3+-F-co-substituted specimen was better than the F-substituted one but worse than the Al3+-substituted one.  相似文献   

13.
(BaxPb1−x)(Zn1/3Nb2/3)O3 (BPZN; x = 0.06–0.1) relaxor ferroelectric ceramics produced using a reaction-sintering process were investigated. Without any calcination involved, the mixture of raw materials was pressed and sintered directly. BPZN ceramics of 100% perovskite phase were obtained. Highly dense BPZN ceramics with a density higher than 98.5% of theoretical density could be obtained. Maximum dielectric constant Kmax 13,500 (at 75 °C), 19,600 (at 50 °C) and 14,800 (at 28 °C) at 1 kHz could be obtained in 6BPZN, 8BPZN and 10BPZN, respectively. Dielectric maximum temperature (Tmax) in BPZN ceramics via reaction-sintering process is lower than BPZN ceramics prepared via B-site precursor route.  相似文献   

14.
We report the electrical conductivity properties of solid-state synthesized perovskite-like La0.8Sr0.2Ga0.8Mg0.2O2.80 (LSGM) and LSGM-SrSn1−xFexO3 (x = 0.8; 0.9) composites. LSGM exhibits both bulk and grain-boundary contribution in the ac impedance plots. The grain-boundary conductivity (σgb) is slightly (≤half-order of magnitude) higher than that of the bulk oxide ion conductivity (σbulk). Powder XRD study reveals that no chemical reaction occurs between LSGM and SrSn1−xFexO3 (1:1 wt.%) at 1000 °C (48 h) and forms a single-phase perovskite-like compound at 1300 °C (48 h) in air, while in hydrogen atmosphere, at 800 °C for 48 h, a growth of LaSrGaO4 and LaSrGa3O7 impurity phases and formation of metallic Fe was observed. The LSGM-SrSn1−xFexO3 (x = 0.8; 0.9) composites show a single or part of semicircle in air at low-temperature regime. The electrical conductivity of the composites were found to be much higher compared to pure LSGM and lower about an order of magnitude than those of pure Sn-doped SrFeO3 perovskite.  相似文献   

15.
The effects of substitution of (Zn1/3Nb2/3) for Ti on the sintering behavior and microwave dielectric properties of Ba3Ti4−x(Zn1/3Nb2/3)xNb4O21 (0 ≤ x ≤ 4) ceramics have been investigated. The dielectric constant (?r) and the temperature coefficient of the resonant frequency (τf) of Ba3Ti4−x(Zn1/3Nb2/3)xNb4O21 ceramics decreased with increasing x. However, the Q × f values enhanced with the substitution of (Zn1/3Nb2/3) for Ti. It was found that a small amount of MnCO3-CuO (MC) and ZnO-B2O3-SiO2 (ZBS) glass additives to Ba3Ti4−x(Zn1/3Nb2/3)xNb4O21 (x = 2) ceramics lowered the sintering temperature from 1250 to 900 °C. And Ba3Ti4−x(Zn1/3Nb2/3)xNb4O21 (x = 2) ceramics with 1 wt% MC and 1 wt% ZBS sintered at 900 °C for 2 h showed excellent dielectric properties: ?r = 53, Q × f = 14,600 GHz, τf = 6 ppm/°C. Moreover, it has a chemical compatibility with silver, which made it as a promising material for low temperature co-fired ceramics technology application.  相似文献   

16.
Electrochemical and thermal properties of Co3(PO4)2- and AlPO4-coated LiNi0.8Co0.2O2 cathode materials were compared. AlPO4-coated LiNi0.8Co0.2O2 cathodes exhibited an original specific capacity of 170.8 mAh g−1 and had a capacity retention (89.1% of its initial capacity) between 4.35 and 3.0 V after 60 cycles at 150 mA g−1. Co3(PO4)2-coated LiNi0.8Co0.2O2 cathodes exhibited an original specific capacity of 177.6 mAh g−1 and excellent capacity retention (91.8% of its initial capacity), which was attributed to a lithium-reactive Co3(PO4)2 coating. The Co3(PO4)2 coating material could react with LiOH and Li2CO3 impurities during annealing to form an olivine LixCoPO4 phase on the bulk surface, which minimized any side reactions with electrolytes and the dissolution of Ni4+ ions compared to the AlPO4-coated cathode. Differential scanning calorimetry results showed Co3(PO4)2-coated LiNi0.8Co0.2O2 cathode material had a much improved onset temperature of the oxygen evolution of about 218 °C, and a much lower amount of exothermic-heat release compared to the AlPO4-coated sample.  相似文献   

17.
The microwave dielectric properties of (BaxMg1−x)(A0.05Ti0.95)TiO3 (A=Zr, Sn) ceramics were investigated with regard to substitution of Ba for Mg of A-site. The microwave dielectric properties were correlated with the Ba content. With an increase in Ba content from 0.01 to 0.1, the dielectric constant and the τf value increased, but the Q×f value decreased. The sintered (BaxMg1−x)(Zr0.05Ti0.95)TiO3 (called BxMZT) ceramics had a permittivity in the range of 19.1−20.6, quality factor from 180,000 to 25,000 GHz, and variation in temperature coefficient of resonant frequency from −35 to −39 ppm/°C with increasing composition x. For sintered (BaxMg1−x)(Sn0.05Ti0.95)TiO3 (called BxMST) ceramics, the dielectric constant increased from 19 to 20.5, Q×f value increased from 120,000 to 37,000 (GHz), and the τf value increased from −50 to −3.3 ppm/°C as the x increased from 0.01 to 0.1. When A=Sn and x=0.1, (Ba0.1Mg0.9)(Sn0.05Ti0.95)TiO3 ceramics exhibited dielectric constant of 20.5, Q×f value of 37,000 (GHz), and a near-zero τf value of −3.3 ppm/°C sintered at 1210 °C for 4 h.  相似文献   

18.
Pr2O3-doped Ba0.85Ca0.15Ti0.90Zr0.10O3 (BCTZ-xPr) ceramics were prepared by the conventional solid-state method. A tetragonal phase is only observed in these ceramics, and the introduction of Pr2O3 decreases their sintering temperature without affecting negatively the piezoelectric constant. Enhanced ferroelectric properties were obtained in these BCTZ-xPr ceramics. The ceramic with x=0.06 wt% exhibits a good electrical behavior of d33∼460 pC/N, kp∼47.6%, εr∼4638, and tan δ∼0.015 when sintered at a low temperature of ∼1400 °C. As a result, the BCTZ-xPr ceramic is a promising candidate for lead-free piezoelectric ceramics.  相似文献   

19.
Gd2(Zr1−xNbx)2O7+x (0 ≤ x ≤ 0.2) ceramics are prepared via the solid state reaction process at 1973 K for 10 h in air. Gd2(Zr1−xNbx)2O7+x (x = 0.1, 0.2) ceramics exhibit an ordered pyrochlore-type structure, whereas Gd2Zr2O7 has a defective fluorite-type structure. The electrical property of Gd2(Zr1−xNbx)2O7+x ceramics is investigated by electrochemical impedance spectroscopy over a frequency range of 10 Hz to 8 MHz from 623 to 923 K. The electrical conductivity obeys the Arrhenius equation. The grain conductivity of Gd2(Zr1−xNbx)2O7+x ceramics varies with doping different Nb contents, and exhibits a maximum at the Nb content of x = 0.1 in the temperature range of 623-923 K. The conductivity in hydrogen atmosphere is a little bit higher than in air in the temperature range of 723-923 K, which indicates that the doping of Zr4+ by Nb5+ can increase the proton-type conduction and reduce the oxide-ionic conduction. The conduction of Gd2(Zr1−xNbx)2O7+x is not a pure oxide-ionic conductor.  相似文献   

20.
The perovskite-like layered structure (PLS) A2B2O7 compound Sr2Nb2O7 was doped with donor dopants CeO2 and WO3 to explore their doping effect on its A and B site, respectively. The doped ceramics were prepared by Spark Plasma Sintering. For Ce doping on the A site, single phase was maintained up to 5 mol% Ce (x=0.05 in (Sr1−xCex)2Nb2O7). For W doping on the B site, single phase was maintained at 2.5 mol% W (x=0.025 in Sr2(WxNb1−x)2O7). The cerium and tungsten doping both inhibited grain growth and changed the grain morphology, leading to less anisotropic grains. The Curie point Tc was obtained by measuring the temperature dependence of the dielectric constant and it was found to reduce for both Ce and W doped SNO. The W doped ceramics showed a diffuse ferroelectric phase transition at the Curie point. The DC resistivity of tungsten and cerium doped SNO increased compared to undoped SNO at temperatures below 700 °C. These results showed that both Ce and W had a strong influence on the dielectric and electrical properties of the Sr2Nb2O7 ceramics.  相似文献   

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