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1.
The attractiveness of Li7La3Zr2O12 (LLZO) cubic based garnets lies in their high ionic conductivity and the combination of thermal and electrochemical stability. However, relations between composition and conductivity as well as degradation effects are still not completely understood. In this contribution we demonstrate the applicability of microelectrodes (Ø = 20–300 μm) for electrochemical impedance spectroscopy (EIS) studies on LLZO garnets. Microelectrodes allow to obtain local information on the ionic conductivity. A comparison between the overall performance of the sample (3.3 × 10?4 S cm?1) and local measurements revealed differences in conductivity with a maximum of the locally measured values of 6.3 × 10?4 S cm?1 and a minimum of 2.6 × 10?4 S cm?1. One reason behind these conductivity variations is most probably a compositional gradient in the sample. In addition, microelectrodes are very sensitive to conductivity changes near to the surface. This was used to investigate the effect of moisture in ambient air on the conductivity variations of LLZO. Substantial changes of the measured Li-ion transport resistance were found, particularly for smaller microelectrodes which probe sample volumes close to the surface.  相似文献   

2.
La2CoTi0.7Mg0.3O6 (LCTM) material has been prepared at 1473 K for 24 h in air. X-ray powder diffraction study has revealed that it contains two orthorhombic perovskite phases (in a ratio ~1:4) with close unit cell parameters. Annealing of LCTM in reducing (Ar/H2, 8%) atmosphere at 1173 K for 12 h has resulted in the preparation of a single-phase material containing the GdFeO3-type perovskite phase with the unit cell parameters of a?=?5.5631(3) Å, b?=?5.5462(3) Å, c?=?7.8522(5) Å. LCTM material exhibits a reversible transformation of a mixture of two perovskite phases with close cation content in air and a single perovskite phase in a reducing atmosphere. Both as-prepared and reduced LCTM samples have been studied by thermogravimetric analysis and dilatometry in air and Ar/H2 (8%). No chemical interaction between the as-prepared LCTM and standard electrolyte materials for SOFC like GDC and YSZ has been observed up to 1273 K. High-temperature electrical conductivity of the as-prepared LCTM at variable oxygen partial pressure (10?4-0.21 atm) showed weak dependence over pO2 with Ea?=?0.48?±?0.01 eV. AC impedance study of the symmetrical cells LCTM/GDC/LCTM has revealed ASR value at 1173 K of ~8.1?±?0.1 Ω?cm2 in air and 0.24?±?0.05 Ω?cm2 in a reducing atmosphere. These results allow to consider LCTM as a promising electrode material for a symmetrical SOFC.  相似文献   

3.
A Ce0.8Sm0.15Ca0.05O1.875 (S15C05DC) sample is synthesized by a solid-state reaction serving as a potential electrolyte material for intermediate-temperature solid oxide fuel cells. The sintered sample was found to be dense with a cubic fluorite structure. The addition of Ca2+ can act as a CeO2 sintering aid for accelerating the process. The microstructures and properties of the sample were analyzed by X-ray diffractometry, Raman spectroscopy, scanning electron microscopy, thermomechanical analysis, and transmission electron microscopy. Existing oxygen vacancies in the sample are indicated by a Raman peak at 558 cm?1. The thermal expansion coefficient of the S15C05DC sample at 200–800 °C is approximately 12–14 × 10?6 °C?1. The control of domain size is an important factor for improving the conductivity of S15C05DC. Local clustered nano-domains, with higher Sm2O3 concentrations, were found to regularly arrange to induce the formation of a nanoscale C-type superlattice structure. While Ca doping decreased the formation of the C-type Sm2O3 structure.  相似文献   

4.
All-solid-state batteries based on fast Li+ conducting solid electrolytes such as Li7La3Zr2O12 (LLZO) give perspective on safe, non-inflammable, and temperature tolerant energy storage. Despite the promise, ceramic processing of whole battery assemblies reaching close to theoretical capacities and finding optimal strategies to process large-scale and low cost battery cells remains a challenge. Here, we tackle these issues and report on a solid-state battery cell composed of Li4Ti5O12 / c-Li6.25Al0.25La3Zr2O12 / metallic Li delivering capacities around 70–75 Ah/kg with reversible cycling at a rate of 8 A/kg (for 2.5–1.0 V, 95 °C). A key aspect towards the increase in capacity and Li+ transfer at the solid electrolyte-electrode interface is found to be the intimate embedding of grains and their connectivity, which can be implemented by the isostatic pressing of cells during their preparation. We suggest that simple adaption of ceramic processing, such as the applied pressure during processing, strongly alters the electrochemical performance by assuring good grain contacts at the electrolyte-electrode interface. Among the garnet-type all-solid-state ceramic battery assemblies in the field, considerably improved capacities and cycling properties are demonstrated for Li4Ti5O12 / c-Li6.25Al0.25La3Zr2O12 / metallic Li pressed cells, giving new perspectives on cheap ceramic processing and up-scalable garnet-based all-solid-state batteries.  相似文献   

5.
0.62Bi(Mg1/2Ti1/2)O3-0.38PbTiO3-xwt%Bi2O3 (BMT-0.38PT-xBi2O3) ceramics were prepared by conventional powder-processing method. It indicated that the morphotropic phase boundary (MPB) region located in 0.0?≤?x?≤?0.3. For x?=?0.3, it exhibited good piezoelectric properties, d33 ~245pC/N and kp ~40 %. With the increase of Bi2O3 content, the Curie temperature (Tc) was found to increase, and the dielectric loss was found to decrease above 200 °C compared with BMT-0.38PT sample. Finally, it can be found that depolarization temperature was around 350 °C by thermal depoling method.  相似文献   

6.
Effects of Ca substitution for Ba on the phase composition, microstructure, sintering behavior and microwave dielectric properties of nominal ceramics Ba1-xCaxV2O6 (0.2?≤?x?≤?0.5) were investigated. The XRD, Raman and SEM results revealed that BaV2O6 and CaV2O6 composite ceramics were formed. Nominal ceramics Ba1-xCaxV2O6 could be well densified at about 550 °C via a solid-state reaction method. The microwave dielectric properties exhibited strong dependence on the composition and microstructure. Typically, the Ba0.7Ca0.3V2O6 ceramics sintered at 550 °C exhibited excellent microwave dielectric properties: εr?=?10.9, Qxf?=?17,100 GHz (at 9.9 GHz), and τf?=?4 ppm/°C. Meanwhile, Ba0.7Ca0.3V2O6 ceramics also showed good chemical compatibility with Al electrode. These results indicated that the Ba0.7Ca0.3V2O6 ceramics could be a promising candidate for the ULTCC technology.  相似文献   

7.
Particulate composites of (1-x) BaTi0.85Sn0.15O3 – x NiFe2O4 (with x?=?5, 10,15 and 20 wt%) were synthesized using the solid-state reaction method by sintering at 1350 °C for 4 h. Formation of the diphase composites was confirmed by X-ray diffraction (XRD) and Fourier Transform Infra-red (FTIR) techniques. Temperature (RT-200 °C) and frequency (20 Hz- 1 MHz) dependent of AC conductivity, dielectric constant and dissipation have been studied. The dielectric constant exhibits strong frequency dispersion in the range 20 Hz-1 kHz which is attributed to Maxwell-Wagner interfacial polarization occurring at grain-grain-boundaries interface/interface of grains of BTS-NF. The M-H curve of all the composites exhibited a hysteresis loops typical charcateistic of a ferromagnetic material. The ferromagnetic ordering in the composites on account of NiFe2O4 as a constituent is explained using bound magnetic polarons (BMPs) model. The experimental magnetic data have been fitted to BMP model. Value of Ms is smaller, whereas of Hc and Mr are higher of the composites compared to value for NiFe2O4. The temperature at which divergence in the M vs. T plot in ZFC and FC starts is higher for the composites than for NiFe2O4.  相似文献   

8.
A K2-mNb2O6-m/2 single crystal with a pyrochlore phase formed when the Nb2O5?+?x mol% KOH specimens with 0.6?≤?x?≤?1.2 were solvothermally heated at 230 °C for 24 h. They have an octahedral shape with a size of 100 μm, and the composition of this single crystal is close to K1.3Nb2O5.65. The single-crystal KNbO3 formed when the single-crystal K2-mNb2O6-m/2 was annealed at a temperature between 600 °C and 800 °C with K2CO3 powders. When annealing was conducted at 600 °C (or with a small amount of K2CO3), the KNbO3 single crystal has a rhombohedral structure that is stable at low temperatures (< ? 10 °C). The formation of the rhombohedral KNbO3 structure can be explained by the presence of the K+ vacancies in the specimen. The KNbO3 single crystal with an orthorhombic structure formed when the K2-mNb2O6-m/2 single crystal was annealed at 800 °C with 20 wt% of K2CO3.  相似文献   

9.
Bi2Sr2-xNaxCo2Oy thermoelectric materials with x = 0, 0.025, 0.05, 0.075, 0.10, 0.125, and 0.15 have been prepared by the classical solid state reaction. Microstructure has shown an important grain growth when Na is added, leading to very high bulk densities confirmed through density measurements. These modifications have produced a drastic decrease of electrical resistivity without significant modification of Seebeck coefficient. As a consequence, Power Factor has been increased in all Na-doped samples, reaching the maximum value (0.21 mW/K2.m at 650 °C) for 0.075 Na samples, which is fairly close to the reported for single crystals.  相似文献   

10.
We prepared NiFe2O4/(Pb, Sr)TiO3 (NFO/PST) bilayer films by the chemical solution method and investigated their multiferroic, magnetoelectric and magneto-impedance properties. Multiferroic properties have been observed at room temperature. The bilayer films exhibit saturation polarization P s ? 26.6 μC/cm2 and saturation magnetization M s ? 134 emu/cm3. With increasing Sr content, M s. and P s values of the NFO/PST bilayer films decrease. The variation may be ascribed to the influence of interfacial strain and decrease in tetragonality. High magnetoelectric coupling effect has been observed in the NFO/PST bilayer films with maximum value of α E  = 6.35 Vcm?1 Oe?1 measured at H DC  ~ 1 kOe and f ~ 10 kHz for Sr ~ 10% (NFO/PST10). The magneto-impedance measurements establish a strong dependence on magnetic field, further confirming magnetoelectric response in NFO/PST bilayer films. An alternative approach for impedance analysis of NFO/PST10 bilayer film provides direct evidence of strain mediated magnetoelectric coupling at room temperature. The results indicate that NFO/PST bilayer films can be considered as a potential multiferroic magnetoelectric material.  相似文献   

11.
The glass-ceramic in the Li2O-Al2O3-SiO2 system has been prepared by melt quenching route. The crystallization kinetics was studied by differential scanning calorimetry. The effects of sintering temperature on the phase transformation, sintering behavior, bulk density, microstructure, thermal expansion, bending strength and dielectric properties were also investigated by X-ray diffractometry and scanning electron microscopy. (Li, Mg, Zn)1.7Al2O4Si6O12 is the first crystalline phase forming in the glass-ceramic and transforms to LiAlSi3O8 phase at 800 °C. The other two crystalline phases of ZrO2 and CaMgSi2O6 precipitate at 700 and 750 °C, respectively. The densification of this LAS glass-ceramic starts at around 730 °C and stops at about 805 °C. The coefficient of thermal expansion increases with the increasing sintering temperature. The sample sintered at 800 °C for 30 min exhibited excellent properties. The nonisothermal activation energy of crystallization is 149 kJ/mol and the values of Avrami constant (n) are in the range of 3.2 to 3.9. The LAS glass-ceramic sintered at 800 °C for 30 min showed excellent properties. This makes that this material suitable for a number of LTCC applications.  相似文献   

12.
BiFeO3-Pb(Mg1/3Nb2/3)O3-PbTiO3 (BF-PMN-PT) ternary ceramics with pure perovskite phase were prepared through a two-step solid reaction method. Based on structural analysis, the ternary phase diagram of BF-PMN-PT solid solution at room temperature has been established. The Curie temperature TC, remnant polarization Pr and piezoelectric constant d33 vary in the range of 138 to 225 °C, 15.12 to 23.65 μC/cm2 and 129 to 276 pC/N, respectively. The coercive field Ec increases gradually from 5.77 to 29.56 kV/cm upon PT content increasing. The magnetic study suggests that the magnetism turns from diamagnetism for PMN-PT to paramagnetism for BF-PMN-PT by adding BiFeO3 into PMN-PT and adding more content of BF does not change the paramagnetism further.  相似文献   

13.
The nanocomposite of Fe2O3-reduced graphene oxide (Fe2O3-RGO) was synthesized by a hydrothermal reduction using self-assembly of Fe(OH)3 colloidal suspension and graphene oxide (GO) as precursors at 180°C. The resulting composites were characterized using XRD, SEM, FTIR, and TGA, and then were used to modify the glassy carbon electrode (GCE). After optimizing the parameters, the electrochemical behavior of honokiol and magnolol on different types of electrode was compared, which indicated that the Fe2O3-RGO composite-modified GCE enhanced electrochemical catalysis effect on the simultaneous determination of honokiol and magnolol. In pH 6.4 PBS solution, two well-shaped oxidation peaks at 0.51 and 0.64 V were observed at the Fe2O3-RGO composite-modified GCE and two well-shaped oxidation peaks were separated absolutely, which eliminated the disturbance between them. A sensitive and simple electrochemical method was proposed for the simultaneous determination of honokiol and magnolol. As to honokiol, the calibration curve is from 1.5 × 10?8 ~ 3.3 × 10?5 M, and the detection limit is 9.64 × 10?9 M. For magnolol, the linear range is from 7.5 × 10?8 ~ 2.6 × 10?5 M, and the detection limit is 1.05 × 10?8 M.  相似文献   

14.
Microwave dielectric properties of low temperature sintering ZnNb2O6 ceramics doped with CuO-V2O5-Bi2O3 additions were investigated systematically. The co-doping of CuO, V2O5 and Bi2O3 can significantly lower the sintering temperature of ZnNb2O6 ceramics from 1150 to 870C. The secondary phase containing Cu, V, Bi and Zn was observed at grain boundary junctions, and the amount of secondary phase increased with increasing CuO-V2O5-Bi2O3 content. The dielectric properties at microwave frequencies (7–9 GHz) in this system exhibited a significant dependence on the relative density, content of additives and microstructure of the ceramics. The dielectric constant ( r) of ZnNb2O6 ceramics increased from 21.95 to 24.18 with increasing CuO-V2O5-Bi2O3 additions from 1.5 to 4.0 wt%. The quality factors (Q× f) of this system decreased with increasing CuO-V2O5-Bi2O3 content and ranged from 36118 to 67100 GHz for sintered ceramics, furthermore, all Q× f values of samples with CuO-V2O5-Bi2O3 additions are lower than that of un-doped ZnNb2O6 ceramics sintered at 1150C for 2 h. The temperature coefficient of resonant frequency ( f) changed from –33.16 to –25.96 ppm/C with increasing CuO-V2O5-Bi2O3 from 1.5 to 4.0 wt%  相似文献   

15.
The n-type polycrystalline Bi2O2Se ceramics were fabricated by solid state reaction and SPSed at different temperatures (873–973 K). The grains of the sample grow up gradually and the grain size enlarges from about 200 nm to micrometer level with the increase of sintering temperature. The highest electrical conductivity of 6.23 S/cm is obtained for the sample sintered at 898 K which benefits from grain orientation along (00l) plane and the highest measured density. The electrical transport properties tend to decline with further increase of the sintering temperature due to the decrease of density and the orientation degree. The maximum power factor of 78.39 μWK?2m?1 is obtained at 773 K. The thermal conductivity is intrinsically suppressed owing to the layered crystal structure of Bi2O2Se and fine grains within the nanometer size. The ZT value reaches 0.09 at 773 K for the sample SPSed at 898 K and the optimal temperature during the SPS process has been determined.  相似文献   

16.
This paper reports re-crystallization behaviour of 60ZnO-30B2O3-10SiO2 pure glass. Influence of different fillers on the re-crystallization is also highlighted. Irrespective of the nature of the filler, glass transition temperature (Tg) remains the same as that of the pure glass at 570 °C. The onset crystallization temperature is enhanced by 15 to 25 °C owing to filler addition. The peak crystallization temperature corresponding to Zn3B2O6, ZnB2O4 and willemite occurs at 735, 810 and 851 °C for the pure glass. In the presence of alumina, gahnite emerges first at 700 °C followed by ZnB2O4 phase. With mullite as filler, initially ZnB2O4 and willemite formed at 700 °C and gahnite phase emerged only at 750 °C and peaks at 787 °C. In the presence of fused silica only ZnB2O4 and willemite phases were observed. The dielectric properties of the pure glass and that of the glass + fillers are also reported. Re-crystallization of various low K phases ensures good dielectric porpertis with reduced glass content after sintenring.  相似文献   

17.
Oxygen nonstoichiometry and the defect chemistry of the SrSn1-xFexO3-x/2+δ (SSF) system were examined by means of thermogravimetry as a function of oxygen partial pressure in the temperature range of 700–1000 °C and compared against the corresponding mixed ionic-electronic conducting titanate, SrTi1-xFexO3-x/2+δ (STF) system. The alternate B site host cation, Sn, was selected to replicate and extend the STF studies, given its distinct band structure and higher electron mobility associated with its 5s derived conduction band as compared to the 3d nature of the conduction band in the titanate. Though shifted slightly by the larger size of Sn, the defect equilibria – including the oxygen vacancy concentration – were found to be largely dominated by Fe oxidation state, and thus differed only in a limited way from those in STF. Key thermodynamic parameters for SrSn0.65Fe0.35O2.825+δ (SSF35) were derived including the reduction enthalpy (4.137 ± 0.175 eV), the high temperature electronic band gap (1.755 ± 0.015 eV) and the anion Frenkel enthalpy (0.350 ± 0.350 eV). The implications these observations have for cathode behavior in solid oxide fuel cells are briefly discussed.  相似文献   

18.
Barium bismuth niobate, Ba(1-x)Bi(2+2x/3)Nb2O9 (BBN with x = 0.0, 0.1, 0.2, 0.3, 0.4) ceramic powders in the nanometer range were prepared by chemical precursor decomposition method (CPD). The single phase layered perovskite was prepared throughout the composition range studied. No intermediate phase was found during heat treatment at and above 600°C. The crystallite size and the particle size, obtained from XRD and TEM respectively, were in the range of 15–30 nm. The addition of Bi2O3 substantially improved the sinterability associated with high density (96%) which was otherwise difficult in the case of pure BaBi2Nb2O9 (BBN x = 0.0). The sintering was done at 900°C for 4 h. The relative permittivity of BBN ceramics at both room temperature and in the vicinity of the temperature of maximum permittivity (Tm) has increased significantly with increase in bismuth content and loss is also decreased to a certain level of bismuth doping. Tm increased with increase in Bi2O3. The diffuseness (γ) in the phase transition was found to increase from 1.54 to 1.98 with the increase in Ba2+ substitution level from x = 0.0 to x = 0.3.  相似文献   

19.
In this study, phase evolution, microstructure, and microwave dielectric properties of (Ba0.98Na0.02)(Mg0.48M3+0.02W0.5)O3 (M3+?=?Al, Ga, Sc, In, Yb, Y, Dy, Gd, and Sm) ceramics sintered at 1700 °C for 1 h were investigated. All the compounds exhibited an ordered cubic perovskite structure. Regardless of the ionic radius of the doped M3+ ions, BaWO4 was detected as the secondary phase in all the compounds. The field emission scanning electron microscopy (FE-SEM) images revealed a dense microstructure in all the compounds, except in the Al-doped compound, which exhibited an insufficient grain growth. The large and irregularly shaped grains indicated that the liquid phase sintering occurred. Splitting of the A1g(O) mode was observed in the Raman spectra of large M3+ ion-doped compounds. Splitting of the F2g modes did not occur and the bands were sharp, indicating that the cubic symmetry was retained. As the ionic radius of the doped M3+ ions increased, the dielectric constant (εr) increased slightly. The compounds doped with M3+?=?Sc, In, Yb, and Y exhibited a very high quality factor (Q?×?f0) in the range of 250,000 ~ 280,000 GHz. In the case of the compounds doped with M3+?=?Al, Ga, Sc, In, Yb, Y, and Dy, the value of the temperature coefficient of resonant frequency (τf) was in the range of ?24 ~ ?19 ppm/°C, while the Gd and Sm-doped compounds exhibited positive values of 2.8 and 31.2 ppm/°C, respectively. The dielectric constant, quality factor, and temperature coefficient of resonant frequency of the In-doped compound, i.e., (Ba0.98Na0.02)(Mg0.48In0.02W0.5)O3, were 18.7, 286,557 GHz, and???24.4 ppm/°C, respectively.  相似文献   

20.
Magnetic-field-assisted electrophoretic deposition method has been employed for synthesizing a(b)-axis-oriented Bi5FeTi3O15 ceramics, and the effects of grain orientation and microstructure on the polarization and piezoelectric properties have been investigated. Grain-oriented Bi5FeTi3O15 ceramics with a high relative sintered density of 98% is shown to exhibit enhanced polarization and piezoelectric properties with a remanent polarization (P r) of 19 μC/cm2 and a piezoelectric strain constant (d 33) of 23 pm/V, which are much superior to those of randomly-oriented ceramics (P r of 7 μC/cm2 and d 33 of 5 pm/V).  相似文献   

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