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1.
Enhancement of oxide-ion conductivity has been investigated with emphasis on the high sintering temperature of apatite-type structure lanthanum silicate (La10Si6O27) as a potential electrolyte for intermediate-temperature solid oxide fuel cells (IT-SOFCs). The influence of the sintering temperatures 1500, 1550, 1600 and 1650 °C as a function of ionic conductivity of the La10Si6O27 electrolyte synthesized via a diethylamine (DEA) precipitation process has been characterized using impedance spectroscopy. The ionic conductivity of the La10Si6O27 electrolyte sintered at 1650 °C revealed a higher value (1.22 × 10−2 S cm−1 at 700 °C) of one order of magnitude than the pellets sintered at lower temperatures. The sintered La10Si6O27 pellets have been characterized by 29Si NMR and Raman spectroscopy. The 29Si NMR data showed the characteristic secondary peak at 81.2 ppm, which confirmed the interstitial oxygen content contributing to high oxide-ion conduction. The Raman spectra revealed the appearance of a new resolved band centered at 861 cm−1 for the pellet sintered at 1650 °C compared with lower temperatures sintered pellets. The results confirmed the possibility of local structural distortion to create additional pathways for interstitial oxide-ion conduction between channels leading to higher conductivity for the pellets sintered above 1600 °C. Thus, the conduction pathway may be determined by the co-operative displacements of the SiO4 substructure units formed at elevated sintering temperatures for high oxide-ion conductivity.  相似文献   

2.
Garnet-type Li7La3Zr2O12 (LLZO) Li+ ion solid electrolyte is a promising candidate for next generation high-safety solid-state batteries. Ga-doped LLZO exhibits excellent Li+ ion conductivity, higher than 1 × 10?3 S cm?1. In this research, the doping amount of Ga, the calcination temperature of Ga-LLZO primary powders, the sintering conditions and the evolution of grains are explored to demonstrate the optimum parameters to obtain a highly conductive ceramics reproducibly via conventional solid-state reaction methods under ambient air sintering atmosphere. Cubic LLZO phase is obtained for Li6.4Ga0.2La3Zr2O12 powder calcined at low temperature 850 °C. In addition, ceramic pellets sintered at 1100 °C for 320 min using this powder have relative densities higher than 94% and conductivities higher than 1.2 × 10?3 S cm?1 at 25 °C.  相似文献   

3.
A Ta-doped Li7La3Zr2O12 (LLZTO) solid electrolyte is a promising candidate for all-solid-state lithium battery due to its high ionic conductivity and stability against lithium metal. In this work, physicochemical properties of both dry- and wet-milled LLZTO particles were investigated. Based on X-ray diffraction, Fourier transform–infrared, thermogravimetric analysis, and scanning electron microscopy results, it was confirmed that highly reactive LLZTO powder prepared in dry milling conditions exhibited faster size reduction, rougher surface morphology, fewer surface impurities, and less agglomerated particles, in contrast to those in wet milling conditions. Sintering these dry-milled powders at 1320°C for 10 min in the air via solid-state reaction produced dense ceramic pellets with a relative density of 97.4%. The room-temperature ionic conductivity for LLZTO pellet via the dry milling was determined to be 6.94 × 10−4 S cm−1. Li–sulfur batteries based on the pellets showed an initial discharge capacity of 1301 mA h g−1 and a coulombic efficiency of 99.82% when cycled at room temperature. The effect of the milled powder on the sintered pellets was discussed in terms of boundary mobility, pore mobility, and morphology.  相似文献   

4.
《Ceramics International》2020,46(8):11508-11514
Nanopowders of holmium zirconate (Ho2Zr2O7) synthesised through carbon neutral sol-gel method were pressed into pellets and individually sintered for 2 h in a single step sintering (SSS) process from 1100 °C to 1500 °C at 100 °C interval and in a two step sintering (TSS) process at (I) −1500 °C for 5 min followed by (II) - 1300 °C for 96 h. Relative density of each of the sintered pellet was determined using the Archimedes’ technique and the theoretical density was calculated from crystal structure data. Grain size was obtained from SEM micrographs using ImageJ. Pellets processed by TSS have been found to be denser (98 %) with less grain growth (1.29 μm) as compared to the pellets processed using SSS process. Ionic conductivity of Ho2Zr2O7 pellets sintered by two different processes was measured using ac impedance spectroscopy technique over the temperature range of 350 °C–750 °C in the frequency range of 100 mHz–100 MHz for both heating and cooling cycles. The temperature dependence of bulk (2.67⨯10−3 Scm−1) and grain boundary (2.50⨯10−3 Scm−1) conductivities of Ho2Zr2O7 prepared by TSS process are greater than those processed by SSS process suggesting the strong influence of processing conditions and grain size. Results of this study, indicates that the TSS is the preferable route for processing the holmium zirconate as it can be sintered to exceptionally high densities at lower temperature, exhibits less grain growth and enhanced ionic conductivity compared with the samples processed by SSS process. Hence, holmium zirconate can be considered as a promising new oxide ion conducting solid electrolyte for intermediate temperature SOFC applications between 350 °C and 750 °C temperature range.  相似文献   

5.
Among the Li-ion conducting inorganic materials, lithium lanthanum zirconate (LLZO) is believed to possess good chemical stability against Li metal and hence considered to be a promising solid electrolyte for Li-ion batteries. However, systematic sets of studies conducted here at regular intervals during storage of Al-doped LLZO (cubic garnet) sintered pellets in ambient atmosphere have raised serious concerns over their structural/mechanical stability/integrity upon exposure to air. Spontaneous cracking/disintegration/pulverization of LLZO pellets takes place after about three weeks of exposure, primarily due to formation of La2Zr2O7 in the LLZO bulk; as found to be thermodynamically feasible at room temperature upon reaction with CO2/moisture. Steep increase in La2Zr2O7 content coincides with the spontaneous cracking/disintegration. Estimation suggests that internal stresses associated with the formation of La2Zr2O7 from LLZO can be high enough to cause spontaneous fracture. This mandates the development/fabrication/usage of solid-state cells using LLZO under stringent controls against exposure to atmospheric species.  相似文献   

6.
《Ceramics International》2017,43(10):7810-7815
Sodium zirconium silicon phosphorus with the composition of Na3Zr2Si2PO12 (NZSP) was prepared by a facile solid state reaction method. The effects of the calcination temperature and rare earth element substitution on the structure and ionic conductivity of the NZSP material were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and AC impedance measurement. The results show that the microstructure and ionic inductivity of the NZSP was strongly affected by the aliovalent substitution of Zr4+ ions in NZSP with rare earth metal of La3+, Nd3+ and Y3+. At room temperature, the optimum bulk and total ionic conductivity of the pure NZSP solid electrolyte sintered under different conditions were 6.77×10−4 and 4.56×10−4 S cm−1, respectively. Substitution of La3+, Nd3+ and Y3+ in place of Zr4+ exhibited higher bulk conductivity compared with that of pure NZSP. Maximum bulk and ionic conductivity value of 1.43×10−3 and 1.10×10−3 S cm−1 at room temperature were obtained by Na3+xZr1.9La0.1Si2PO12 sample. The charge imbalance created by aliovalent substitution improves the mobility of Na+ ions in the lattice, which leads to increase in the conductivity. AC impedance results indicated that the total ionic conductivity strongly depends on the substitution element and the feature of the grain boundary.  相似文献   

7.
《Ceramics International》2023,49(12):19905-19915
Cubic Li6.4La3Zr1.4Ta0.6O12 (c-LLZTO) electrolyte is one of the most promising solid electrolytes. However, it is rather difficult to promote its electrical performance while reducing process parameters. Therefore, Li4GeO4 is applied as the additive in liquid sintering of LLZTO ceramics in this study. The LLZTO@Li4GeO4/Li2O composite electrolyte sintered at 1180 °C for 3 h performs a significantly promoted microstructure and electrical performance, the ionic conductivity of which reaches 5.77 × 10−4 S cm−1 at 25 °C. The Li4GeO4/Li2O eutectic phase contributed prominently, in which the high concentration of Li+ seaming the LLZTO grains tightly. Meanwhile, Li+ conduction in the consecutive conductive pathways constructed by [GeO4] groups among the grains was greatly stimulated. With the modification of the grain boundary, an improved garnet electrolytes/Li anode interface performance is produced. The Li/Au|LLZTO@Li4GeO4/Li2O|Au/Li symmetrical cell is able to cycle stably for more than 500 h at the current density of 0.1 mA cm−2 at room temperature.  相似文献   

8.
《Ceramics International》2016,42(10):12156-12160
Li7La3Zr2O12 (LLZO) has cubic garnet type structure and is a promising solid electrolyte for next-generation Li-ion batteries. In this work, Al-doped LLZO was prepared via conventional solid-state reaction. The effects of sintering temperature and Al doping content on the structure and Li-ion conductivity of LLZO were investigated. The phase composition of the products was confirmed to be cubic LLZO via XRD. The morphology and chemical composition of calcined powders were investigated with SEM, EDS, and TEM. The Li-ion conductivity was measured by AC impedance. The results indicated the optimum sintering temperature range is 800–950 °C, the appropriate molar ratio of LiOH·H2O, La(OH)3, ZrO2 and Al2O3 is 7.7:3:2:(0.2–0.4), and the Li-ion conductivity of LLZO sintered at 900 °C with 0.3 mol of Al-doped was 2.11×10−4 S cm−1 at 25 °C.  相似文献   

9.
Solid Oxide Fuel Cells (SOFCs) are environmentally efficient energy conversion devices, but are partially limited by the complicated fabrication procedure. In this work, dense 8 mol% yttria-stabilized zirconia (8YSZ) ceramics were successfully realized through a DLP (digital light processing) stereolithography method and the electrolyte self-supported fuel cell was also tested at 800 °C. The sintering behavior of the as-printed planar samples were investigated and a fully dense ceramic can be achieved at 1450 °C. The total conductivity of the sintered 8YSZ can reach 2.18 × 10−2 S cm−1 at a test temperature of 800 °C, which is acceptable for practical application. For the electrolyte self-supported fuel cell test, a power density of 114.3 mW cm−2 can be achieved when Ni-8YSZ cermet and La0.8Sr0.2MnO3 (LSM) were used as anode and cathode. It was demonstrated that 3D printing is a promising processing technique to build up electrolyte self-supported SOFCs with desired structure for the future development.  相似文献   

10.
S. Li  H. Tu  L. Yu  M. T. Anwar 《Fuel Cells》2016,16(6):822-828
A novel fabrication process for solid oxide fuel cells (SOFCs) with La0.2Sr0.7TiO3–δ (LSTA–) as anode support and La2NiO4+δ (LNO) as cathode material, which avoids complicated impregnation process, is designed and investigated. The LSTA– anode‐supported half cells are reduced at 1,200 °C in hydrogen atmosphere. Subsequently, the LNO cathode is sintered on the YSZ electrolyte at 1,200 °C in nitrogen atmosphere and then annealed in situ at 850 °C in air. The results of XRD analysis and electrical conductivity measurement indicate that the structure and electrochemical characteristics of LNO appear similar before and after the sintering processes of the cathode. By using La0.6Sr0.4CoO3–δ (LSC) as current collector, the cell with LNO cathode sintered in nitrogen atmosphere exhibits the power density at 0.7 V of 235 mW cm−2 at 800 °C. The ohmic resistance (RS) and polarization resistance (RP) are 0.373 and 0.452 Ω cm2, respectively. Compared to that of the cell with the LNO cathode sintered in air, the sintering processes of the cell with the LNO cathode sintered in nitrogen atmosphere can result in better electrochemical performance of the cell mainly due to the decrease in RS. The microstructures of the cells reveal a good adhesion between each layer.  相似文献   

11.
Metal-supported solid oxide fuel cells (MS-SOFCs) have been fabricated by applying phase-inversion tape-casting and atmospheric plasma spraying (APS). The effect of the binder amount of the phase-inversion slurries on the microstructure development of the 430L stainless steel metal support was investigated. The pore structures, the viscosity of the slurry, porosity and permeability of the as-prepared metal supports are significantly influenced by the amount of the binder. NiO–scandia-stabilized zirconia (ScSZ) anode, ScSZ electrolyte and La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) cathode layers were consecutively deposited on the metal support with an ideal microstructure by APS process. The effect of plasma power of the APS on the microstructure of the electrolyte and cathode was investigated. A dense electrolyte layer and a porous cathode layer were successfully obtained at 40 and 6 kW of the APS plasma power, respectively. MS-SOFCs, with a cell configuration of 430L/Ni-ScSZ/ScSZ/LSCF, achieved a maximum cell power density of 1079 mW cm−2 at 700°C using humidified H2 as fuel and ambient air as oxidant. The corresponding ohmic resistance and total resistance of MS-SOFCs was 0.14 and 0.32 Ω cm2, respectively. This work demonstrates the feasibility of fabricating high-performance MS-SOFCs with economical and scalable techniques.  相似文献   

12.
La‐doping mechanisms and thermoelectric properties of Sr3Ti2O7 Ruddlesden–Popper (RP) ceramics sintered under air and flowing 5% H2 at 1773 K for 6 h have been investigated. Changes in lattice parameters and conductivity revealed a limited interstitial anion mechanism (~1 at.%) based on La3+ + ½O2?→Sr2+, which resulted in insulating samples when processed in air. In contrast, electronic donor‐doping (La3+ + e? → Sr2+) and oxygen loss [O2? → ½ O2 (g) + 2 e?] are the dominant mechanism(s) in 5% H2‐sintered ceramics with a solution limit of ~5 at.%. The increased solubility limit is attributed to the formation of Ti3+ during reduction, which compensates for the extra positive charge associated with La on the A‐site and also to the occurrence of oxygen loss due to the reducing conditions. For 5% H2‐sintered samples, an insulating surface layer was formed associated with SrO volatilization and oxygen uptake (during cooling) from the sintering. Unless removed, the insulating layer masked the conductive nature of the ceramics. In the bulk, significantly higher power factors were obtained for ceramics that were phase mixtures containing highly conductive perovskite‐based (Sr,La)TiO3?δ (ST). This highlights the superior power factor properties of reduced perovskite‐type ST phases compared to reduced RP‐type Sr3Ti2O7 and serves as a precaution for the need to identify low levels of highly conducting perovskite phases when exploring rare‐earth doping mechanisms in RP‐type phases.  相似文献   

13.
《Ceramics International》2020,46(6):7741-7747
Solid electrolytes with high lithium-ion conductivity and superior stability are key components in the development of all-solid-state lithium-ion batteries. In this study, novel quaternary solid electrolytes Li2x-ySr1-x-yLayTiO3 (x = 3y/4, y = 1/7, 2/7, 3/7, 1/2, 15/28, and 4/7) were synthesized by conventional solid-state reaction approach. X-ray diffraction analysis revealed that with the increase in La3+ content, Li2x−ySr1−x−yLayTiO3 structure changes from cubic to tetragonal perovskite-type structure. Electrochemical impedance spectroscopy revealed that with the increase in y-value, enhanced conductivity was initial observed, followed by a decrease. Li15/56Sr1/16La15/28TiO3 electrolyte exhibited optimal total Li-ion conductivity of 4.84 × 10−4 S cm−1, electronic conductivity of 6.84 × 10−10 S cm−1, and activation energy of 0.29 eV. On the other hand, cyclic voltammetry revealed unstable Li1/8Sr1/8La1/2TiO3, Li15/56Sr1/16La15/28TiO3, and Li2/7La4/7TiO3 specimens at voltages of less than ~2 V, indicative of their incompatibility with lithium metal or Li4Ti5O12 in all-solid-state batteries. Charge-discharge tests confirmed the utility of electrolytes as solid separators with good performance in semi-solid-state batteries. Overall, these results are beneficial for future research on solid electrolytes and their applications in all-solid-state lithium-ion batteries.  相似文献   

14.
We investigated the sintering temperature dependency on the properties of Na2Zn2TeO6 (NZTO) solid electrolyte synthesized via a conventional solid-state reaction method. Sintering temperature of calcined NZTO powder, which was obtained by the calcination of precursor at 850℃, was changed in the range from 650 to 850℃. X-ray diffraction analysis showed that P2-type layered NZTO phase was formed in all sintered samples without forming any secondary phases. The relative densities of sintered NZTO samples were approximately 83%−85% for the samples sintered at 700℃ or higher. The all sintered samples showed sodium-ion conductivity above 10−4 S cm−1 at room temperature and the highest conductivity of 4.0 × 10−4 S cm−1 in the sample sintered at 750℃. The sintering temperature to obtain the highest room temperature conductivity is 100℃ lower than that used in previous works. Such low sintering temperature compared to other Na-based oxide solid electrolytes could be useful for co-sintering with electrode active materials for fabrication of all-solid-state sodium-ion battery.  相似文献   

15.
《Ceramics International》2017,43(4):3847-3853
La9.33Si2Ge4O26 materials have been fabricated from La2O3, SiO2 and GeO2 powders by high speed mechanical alloying followed by conventional and microwave hybrid sintering at different temperatures and holding times. XRD data showed that the apatite phase is formed after 1 h of mechanical alloying at 850 rpm. This phase remained stable after conventional sintering in an electric furnace with density increasing as sintering temperatures and holding times were increased. However, the highest density was achieved for samples sintered in the microwave furnace (5.44 g cm−3), corresponding to a relative density of 98%. The electrical conductivity of the samples microwave sintered at 700 and 800 ºC are 4.72×10−3 and 1.93×10−2 S.cm−1, respectively, with a correspondent activation energy of 0.952 eV.  相似文献   

16.
Cobalt − free perovskite oxide La0.5Ba0.5Fe0.95Mo0.05O3−δ (LBFMo) was investigated as the electrode of symmetric solid oxide fuel cell (S − SOFC) based on 300−um − thick La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM) electrolyte. The electrochemical performance of the S − SOFC with LBFMo|LSGM|LBFMo configuration was evaluated using ambient air as oxidant and H2 as fuel. The maximum power density (Pmax) of the S − SOFC achieves as high as 0.96 W cm−2 at 800 °C; meanwhile, the total polarization resistance (Rpt) of the S − SOFC (including the contributions of both cathode and anode) is only ∼0.12 Ω cm2. Impedance spectra analysis indicates the polarization associated with anode plays a more rate − limiting role in the whole electrochemical reaction process of the S − SOFC. In addition, using LBFMo as symmetric electrode, the S − SOFC also exhibits good cell stability. All results indicate that the LBFMo is a very potential candidate for S − SOFC electrode.  相似文献   

17.
This work explores a chemical synthesis route and, for the first time, laser processing of ionic conductor Li0.5La0.5TiO3 (LLTO) ceramics. The laser sintering technique has been efficient in producing highly dense single-phase ceramics in just a few minutes, starting from an amorphous precursor powder. As comparison, conventionally sintered ceramics were also prepared. Both methods yield polycrystals with long-range structure compatible with a single cubic perovskite, as confirmed by Rietveld refinement of the powder XRD pattern. In contrast, Raman spectroscopy has revealed non-cubic symmetry, indicating the formation of ordered nanodomains. At room temperature, high ionic conductivity of ∼0.5 mS/cm was achieved for the bulk of laser and conventionally sintered samples. However, the grain boundary conductivity changed from 1⋅10−3 mS⋅cm−1 (laser-sintered) to 6⋅10−3 mS⋅cm−1 (conventionally sintered), which was attributed to changes in the microstructural characteristics of the ceramics.  相似文献   

18.
《Ceramics International》2020,46(3):3367-3373
Lithium lanthanum zirconate (Li7La3Zr2O12, LLZ) solid electrolytes were usually prepared by using Al2O3 crucibles and/or Al3+ dopants in order to stablize the formation of cubic garnet phase. In this work, we argue that Al-free MgO crucible could be better for the preparation of LLZ-based solid electrolytes through a detailed comparison of LLZ-Ga0.2 samples prepared respectively by using MgO and Al2O3 crucibles. The solid-state reaction method was firstly used to prepare Li7-3xGaxLa3Zr2O12 (x = 0–0.4) pellets by using Al-free MgO crucibles, which were sintered at 1100 °C for 12 h. The highly conductive cubic phase was obtained at Ga3+ doping content as low as x = 0.05 and the highest room-temperature conductivity was obtained at x = 0.2. Al2O3 crucible was then used to prepare the LLZ-Ga0.2 pellet for comparing the influence of these two different crucibles. The results show that a higher lattice parameter (a = 12.9762 (8) Å), a higher relative density (95.5%) and a higher room-temperature ionic conductivity (1.352 (3) mS/cm) were achieved by using the MgO crucible.  相似文献   

19.
C. Fu  X. Ge  S. H. Chan  Q. Liu 《Fuel Cells》2012,12(3):450-456
Large‐size, 9.5 cm × 9.5 cm, Ni‐Gd0.1Ce0.9O1.95 (Ni‐GDC) anode‐supported solid oxide fuel cell (SOFC) has been successfully fabricated with NiO‐GDC anode substrate prepared by tape casting method and thin‐film GDC electrolyte fabricated by screen‐printing method. Influence of the sintering shrinkage behavior of NiO‐GDC anode substrate on the densification of thin GDC electrolyte film and on the flatness of the co‐sintered electrolyte/anode bi‐layer was studied. The increase in the pore‐former content in the anode substrate improved the densification of GDC electrolyte film. Pre‐sintering temperature of the anode substrate was optimized to obtain a homogeneous electrolyte film, significantly reducing the mismatch between the electrolyte and anode substrate and improving the electrolyte quality. Dense GDC electrolyte film and flat electrolyte/anode bi‐layer can be fabricated by adding 10 wt.% of pore‐former into the composite anode and pre‐sintering it at 1,100 °C for 2 h. Composite cathode, La0.6Sr0.4Fe0.8Co0.2O3, and GDC (LSCF‐GDC), was screen‐printed on the as‐prepared electrolyte surface and sintered to form a complete single cell. The maximum power density of the single cell reached 497 mW cm–2 at 600 °C and 953 mW cm–2 at 650 °C with hydrogen as fuel and air as oxidant.  相似文献   

20.
In the present study, we investigate the fundamental properties of CeO2 by selecting La3+ (57), and Dy3+ (66) as dopants with optimized average atomic number of 61.5, which lies in between Pm3+ (62) and Sm3+ (62) in accordance with the criteria for optimum doping. A system of co-doped ceria ceramics Ce1–x–yLaxDyyO2-δ ((x, y) = (0.00, 0.00), (0.025, 0.025), (0.05, 0.05), (0.075, 0.075), (0.10, 0.10), (0.00, 0.20) and (0.20, 0.00)) as electrolytes for intermediate temperature solid oxide fuel cells were successfully prepared by a well-known sol-gel auto-combustion route. In order to obtain dense samples, the prepared pellets were sintered in air at 1300 °C for 4 h using conventional furnace and relative densities of all the samples were found to be higher than 95%. Single phase cubic structure, microstructural density and elemental composition analysis of all the samples were studied by powder X-ray diffraction, scanning electron microscope and energy dispersive spectroscopy techniques, respectively. Raman spectroscopy analysis confirmed the formation of concentrated O2-–vacancies in the co-doped ceria system. Impedance spectroscopy measurements revealed the high value of total ionic conductivity and low activation energy for the composition Ce0.85La0.075Dy0.075O2?δ i.e., 2.08 × 10–2 S cm–1 and 0.58 eV, respectively. Linear thermal expansion analyses of all the samples revealed the matched thermal expansion coefficients. Finally, these results recommend that the Ce0.85La0.075Dy0.075O2?δ sample can be useful as a solid electrolyte in IT-SOFC applications.  相似文献   

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