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1.
The electrochemical performances of Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag composite cathodes have been investigated in intermediate temperature solid oxide fuel cells. The Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag cathodes prepared by ball milling followed by firing at 920 °C show the maximum performance (power density: 0.15 W cm−2 at 800 °C) at 3 wt.% Ag. On the other hand, the Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag composite cathodes with 0.1 mg cm−2 (0.5 wt.%) Ag that were prepared by an impregnation of Ag into Nd0.6Sr0.4Co0.5Fe0.5O3−δ followed by firing at 700 °C (but the electrolyte–Nd0.6Sr0.4Co0.5Fe0.5O3−δ assembly was prepared first by firing at 1100 °C) exhibit much better performance (power density: 0.27 W cm−2 at 800 °C) than the composite cathodes prepared by ball milling, despite a much smaller amount of Ag due to a better dispersion and an enhanced adhesion. AC impedance analysis indicates that the Ag catalysts dispersed in the porous Nd0.6Sr0.4Co0.5Fe0.5O3−δ cathode reduce the ohmic and the polarization resistances due to an increased electronic conductivity and enhanced electrocatalytic activity.  相似文献   

2.
The cathode is a key component in low temperature solid oxide fuel cells. In this study, composite cathode, 75 wt.% Sm0.5Sr0.5CoO3 (SSC) + 25 wt.% Sm0.2Ce0.8O1.9 (SDC), was applied on the cermet supported thin SDC electrolyte cell which was fabricated by tape casting, screen-printing, and co-firing. Single cells with the composite cathodes sintered at different temperatures were tested from 400 to 650 °C. The best cell performance, 0.75 W cm−2 peak power operating at 600 °C, was obtained from the 1050 °C sintered cathode. The measured thin SDC electrolyte resistance Rs was 0.128 Ω cm2 and total electrode polarization Rp(a + c) was only 0.102 Ω cm2 at 600 °C.  相似文献   

3.
Mesoporous Ce0.8Sm0.2O1.9 (SDC) oxide with high surface area was prepared by a novel glycine-nitrate combustion process with in situ created nickel oxide as template, and applied as the catalytic layer for methane-fueled solid-oxide fuel cells (SOFCs) operated at reduced temperatures. The weight ratio of nickel oxide to SDC in the synthesis process was found to have significant effect on both the crystallite size and the textural properties of the resulted SDC powder. In particular, when it was at 9, the thermally stable and well-crystallized SDC powder showed a mesoporous structure with narrow pore-size distribution, high surface area (77 m2 g−1) and large pore volume (0.2276 cm3 g−1), even after the calcination at 700 °C for 3 h. The mesoporous SDC was found to favor free gas diffusion with no gas diffusion polarization occurred even at high current density both for hydrogen and methane fuels. The SOFC with Ru impregnated mesoporous SDC catalytic layer displayed promising performance with a peak power density of 462 mW cm−2 at 650 °C.  相似文献   

4.
LiNi0.5Co0.44Fe0.06VO4 cathode material has been synthesized by a citric acid:polyethylene glycol polymeric method at 723 K for 5 h in air. The surface of the LiNi0.5Co0.44Fe0.06VO4 was coated with various wt.% of Al2O3 by a wet chemical procedure and heat treated 873 K for 2 h in air. The samples were characterized by XRD, FTIR, SEM, and TEM techniques. XRD patterns expose that the complete crystalline phase occurred at 723 K and there was no indication of new peaks for the coated samples. FTIR spectra show that the complete removal of organic residues and the formation of LiNi0.5Co0.44Fe0.06VO4. TG/DTGA results reveal that the formation of LiNi0.5Co0.44Fe0.06VO4 occurred between 480 and 670 K and the complete crystalline occurred at 723 K. SEM micrographs show the various morphological stages of the polymeric intermediates. TEM micrographs of the pristine LiNi0.5Co0.44Fe0.06VO4 reveal that the particle size ranged from 130 to 150 nm and Al2O3 coating on the fine particles was compact and had an average thickness of about 15 nm. The charge–discharge experiments were carried out between 2.8 and 4.9 V (versus Li) at a current rate of 0.15 C. The 1.0 wt.% Al2O3 coated sample had the best electrochemical performance, with an initial capacity of 65 mAh g−1 and capacity retention of 60% after 50 cycles. The electrochemical impedance behavior suggests that the failure of pristine cathode performance is associated with an increase in the impedance growth on the surface of the cathode material upon continuous cycling.  相似文献   

5.
The elastic moduli, i.e., Young’s modulus, shear modulus and Poisson’s ratio, of a sintered La0.9Sr0.1Ga0.8Mg0.2O3−δ bulk have been experimentally determined in the temperature range from room temperature to 1373 K using a resonance technique. Anomalous elastic properties were observed over a wide temperature range from 473 to 1173 K. In the results for internal friction and in X-ray diffraction measurements at elevated temperature, two varieties of structural changes were seen in La0.9Sr0.1Ga0.8Mg0.2O3−δ in the examined temperature range. The results agreed with the findings of a previous crystallographic study of the same composition system by Slater et al. In addition, the temperature range in which a successive structural change occurred in La0.9Sr0.1Ga0.8Mg0.2O3−δ was the same as that exhibiting the anomalous elastic properties. Taking all the results together, it can be inferred that the successive structural change in the significant temperature range is responsible for the elastic property anomaly of La0.9Sr0.1Ga0.8Mg0.2O3−δ.  相似文献   

6.
The preparation of LiCoyMnxNi1−xyO2 from LiOH·H2O, Ni(OH)2 and γ-MnOOH in air was studied in detail. Single-phase LiCoyMnxNi1−xyO2 (0y0.3 and x=0.2) is obtained by heating at 830–900°C. The optimum heating temperatures are 850°C for y=0–0.1 and 900°C for y=0.2–0.3. Excess lithium (1z1.11 for y=0.2) and the Co doping level (0.05y0.2) do not significantly affect the discharge capacity of LizCoyMn0.2Ni0.8−yO2. The doping of Co into LiMn0.2Ni0.8O2 accelerates the oxidation of the transition metal ion, and suppresses partial cation mixing. Since the valence of the manganese ion in LiMn0.2Ni0.8O2 is determined to be 4, the formation of a solid solution between LiCoyNi1−yO2 and Li2MnO3 is confirmed.  相似文献   

7.
Layered LiAl1/3−xCoxNi1/3Mn1/3O2 (0  x  1/3) compounds were studied via the combination of computational and experimental approach. The calculated voltage curve of LiNi1/3Al1/3Mn1/3O2 compound is presented, indicating it is of great potential for a cathode material of lithium-ion batteries. Unfortunately, it was found that the LiNi1/3Al1/3Mn1/3O2 compound without impurity phase could not be synthesized via a sol–gel process. To obtain a layered compound without impurity phase, partial of Al is replaced by Co in LiNi1/3Al1/3Mn1/3O2 compound in this study. Layered LiAl1/3−xCoxNi1/3Mn1/3O2 (0  x  1/3) compounds were synthesized via sol–gel reaction at 900 °C under a oxygen stream. Single phase of the LiAl1/3−xCoxNi1/3Mn1/3O2 in 1/6  x  1/3 region could be prepared successfully. The discharge capacity and conductivity increased with an increase in the Co-substitution content. The enhancement of the conductivity and phase purity by the introduction of Co content shows profound influence on the performance of the LiAl1/3−xCoxNi1/3Mn1/3O2 compounds.  相似文献   

8.
制备锂离子电池正极材料LiNi0.8Co0.2O2通常需要在纯氧气气氛下进行烧结.本工作以硫酸镍,硫酸钴和氢氧化钠为原料,采用并流共沉淀法制备了高密度Ni0.8Co0.2(OH)2前驱体,再采用高温固相反应法在空气中烧结制备了锂离子电池LiNi0.8Co0.2O2正极材料.采用X射线衍射(XRD),扫描电镜(SEM),恒流充放电测试(ECT),循环伏安(CV)与比表面积(BET)测试等方法对目标样品进行了表征,详细考察了烧结条件对材料结构,微观形貌及电化学性能的影响.结果表明,锂/(钴+镍)摩尔比为1.13∶1时,在管式炉中和空气气氛下于第一段烧结温度700 ℃保温9 h,于第二段烧结温度750 ℃保温12 h,合成的材料比表面积适中(0.78 m2/g),具有规则的六边形α-NaFeO2层状结构,晶粒分布均匀,电化学性能最优.在0.5 C充放电倍率下和2.7~4.3 V电压范围内,其首次放电比容量达到153.0 mA·h/g,循环20次后放电比容量仍为150.7 mA·h/g,容量保持率达到98.5%,显示了优异的循环稳定性能,可用做高能量密度动力电池正极材料.  相似文献   

9.
The solid solutions of CexSn1−xO2 incorporated with alumina to form CexSn1−xO2–Al2O3 mixed oxides, by the suspension/co-precipitation method, were used to prepare CuO/CexSn1−xO2–Al2O3 catalysts for the selective oxidation of CO in excess hydrogen. Incorporating Al2O3 increased the dispersion of CexSn1−xO2, but did not change their main structures and did not weaken their redox properties. Doping Sn4+ into CeO2 increased the mobility of lattice oxygen and enhanced the activity of the 7%CuO/CexSn1−xO2–Al2O3 catalyst in the selective oxidation of CO. The selective oxidation of CO was weakened as the doped fraction of Sn4+ exceeded 0.5. Incorporating appropriate amounts of Sn4+ and Al2O3 could obtain good candidates 7%CuO/CexSn1−xO2–Al2O3(20%), 1–x=0.1–0.5, for a preferential oxidation (PROX) unit in a polymer electrolyte membrane fuel cell system for removing CO. Its activity was comparable with, and its selectivity was much larger than, that of the noble catalyst 5%Pt/Al2O3.  相似文献   

10.
《Solar Energy》2000,68(6):523-540
Layered LixCoO2 and LixNiO2 thin films (x1) were prepared by a peroxo wet chemistry route from Li(I), Co(II) and Ni(II) acetate precursors and the addition of H2O2. Structural changes during the processing of xerogel to final oxide were followed by X-ray diffraction and infrared spectroscopy. Electrochromic properties were determined with in-situ potentiodynamic, potentiostatic and galvanostatic spectroelectrochemical measurements. Single dipped films with composition Li0.99Co1.01O2 or Li0.94Ni1.06O2 exhibited stable voltammetric response in 1 M LiClO4/propylene carbonate electrolyte after about 60 cycles. The total charge exchanged in a reversible charging/discharging cycle was about ±30 mC cm−2 for Li0.99Co1.01O2 and ±20 mC cm−2 for Li0.94Ni1.06O2 oxide films. Galvanostatic measurements showed that about 1/2 (x0.5) and 2/3 (x0.3) of Li+ ions could be reversibly removed from the structure of Li0.99Co1.01O2 and Li0.94Ni1.06O2 films, respectively. Practical applicability of Li0.99Co1.01O2 and Li0.94Ni1.06O2 oxide films was studied in electrochromic devices with WO3(H+)Li+ormolyteLi0.99Co1.01O2 and WO3(H+)Li+ormolyteLi0.94Ni1.06O2 configuration. The monochromatic transmittance Ts (λ=633 nm) of dark blue coloured devices was extremely low (Ts3%), whereas in bleached state the value reached around Ts70%.  相似文献   

11.
LiNi1/3Mn1/3Co1/3O2 prepared by a spray drying method exhibited poor cyclic performance when it was operated at rates of 0.5C and 2C in 3–4.6 V. A metal oxide (ZrO2, TiO2, and Al2O3) coating (3 wt%) could effectively improve its cyclic performance at both 0.5C and 2C. Electrochemical impedance spectroscopy (EIS) studies suggested that both the surface resistance and the charge transfer resistance of the bare LiNi1/3Mn1/3Co1/3O2 significantly increase after 100 cycles, whose origin is mainly related to the change in both the particle surface and electrode morphologies. The presence of a thin metal oxide layer could remarkably suppress the increase in the total resistance (sum of the surface resistance and the charge transfer resistance), which was attributed to the improvement in good cyclic performances.  相似文献   

12.
A comparative analysis of the properties of LiNi0.5Mn0.5O2 and Li1+xNi0.5Mn0.5O2 (0.2 ≤ x ≤ 0.7) powders, obtained by the freeze drying method, was performed. Lattice parameters of Li1+xNi0.5Mn0.5O2 decreased considerably with growing amounts of Li until x = 0.3; at x > 0.5 trace amounts of Li2MnO3 are observed by X-ray diffraction (XRD) patterns. X-ray photoelectron spectroscopy (XPS) analysis displayed an increase of Ni3+/Ni2+ ratio at 0.3 < x < 0.5, while Mn 2p spectra were almost identical in all samples. Rechargeable capacity values (V = 2.5–4.6 V) increased systematically with x reaching its maximum (185–190 mAh g−1) at x = 0.5. Samples with superstoichiometric lithium content also demonstrated good C rate characteristics.  相似文献   

13.
Thermogravimetry was used to study the oxidation of aluminum powders at elevated temperatures. Aluminum powders of various particle sizes and surface morphologies were heated in oxygen up to 1500 °C at different heating rates. Partially oxidized samples were recovered from selected intermediate temperatures and the oxide phases present were analyzed by X-ray diffraction. The experimental data were related to current information on stabilities and phase changes of Al2O3 polymorphs. Aluminum powders were observed to oxidize in four distinct stages in the temperature range from 300 to 1500 °C. During stage I, from 300 to about 550 °C, the thickness of the natural amorphous alumina layer on the particle surface increases. The rate of this process is controlled by the outward diffusion of Al cations. At about 550 °C, when the oxide layer thickness exceeds the critical thickness of amorphous alumina of about 4 nm, the oxide transforms into γ-Al2O3. The specific volume of γ-Al2O3 is less than that of amorphous alumina; therefore, the newly formed γ-Al2O3 only partially covers the aluminum surface. The oxidation rate increases rapidly at the onset of stage II, but it decreases when the γ-Al2O3 layer becomes continuous. During stage III oxidation, the γ-Al2O3 layer grows and partially transforms into the structurally similar θ-Al2O3 polymorph. Finally, oxidation stage IV is observed after the transition to stable -Al2O3 results in an abrupt reduction of oxidation rate. Qualitative analysis of the rates of oxidation at the different stages enables one to understand the wide range of aluminum ignition temperatures observed for particles of different sizes.  相似文献   

14.
为了改善LiNi0.8Co0.15Al0.05O2正极材料的电化学热稳定性能,加入LiFePO4共混制成了LiFePO4/LiNi0.8Co0.15Al0.05O2锂离子电池用混合正极材料。使用X射线衍射(XRD)和扫描电子显微镜(SEM)表征了结构和形貌,测试了电化学性能。结果显示,简单球磨的混合LiFePO4/LiNi0.8Co0.15Al0.05O2正极材料中,纳米LiFePO4粒子包覆在LiNi0.8Co0.15Al0.05O2粒子表面提高了混合正极材料在充放电过程中的电化学稳定性和结构稳定性。LiFePO4/LiNi0.8Co0.15Al0.05O2混合正极材料在50 ℃下循环100周容量保持率为82.0%,明显地优于单一LiNi0.8Co0.15Al0.05O2材料的72.9%。  相似文献   

15.
This study presents the electrochemical performance of (Ba0.5Sr0.5)0.9Sm0.1Co0.8Fe0.2O3−δ (BSSCF) as a cathode material for intermediate temperature solid oxide fuel cells (IT-SOFC). AC-impedance analyses were carried on an electrolyte supported BSSCF/Sm0.2Ce0.8O1.9 (SDC)/Ag half-cell and a Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF)/SDC/Ag half-cell. In contrast to the BSCF cathode half-cell, the total resistance of the BSSCF cathode half-cell was lower, e.g., at 550 °C; the values for the BSSCF and BSCF were 1.54 and 2.33 Ω cm2, respectively. The cell performance measurements were conducted on a Ni-SDC anode supported single cell using a SDC thin film as electrolyte, and BSSCF layer as cathode. The maximum power densities were 681 mW cm−2 at 600 °C and 820 mW cm−2 at 650 °C.  相似文献   

16.
《Solar Energy》2000,68(6):209-515
Various mixed Fe/V-oxides can be used as anodes in Li+ rocking chair batteries, however, their small optical modulation during the insertion/extraction of Li+ ions makes them candidates for the counter electrodes in electrochromic (EC) devices. The sol–gel route in combination with dip-coating deposition was used for the preparation of Fe/V-oxide films with molar ratios Fe:V=0.1:1, 1:2, 1:1 and 2:1. X-ray diffraction combined with Fourier transform infrared (FT-IR) spectroscopy studies of films and powders reveal that heating of xerogel films at 400°C produces films with nanosized FeVO4 (Fe:V=1:1) and Fe2V4O13 (Fe:V=1:2) grains, while the corresponding crystalline powders were obtained at 500°C (8 h). Charge capacities (Q) of Fe/V-oxide films (300 and 400°C) were determined using cyclic voltammetry (CV) from 1.5 to −1.5 V vs. Ag/AgCl (4.8 to 1.8 V vs. Li) in 1 M LiClO4/propylene carbonate (PC) electrolyte. Our results revealed that Q values of Fe/V-oxide films are up to 20 mC cm−2 depending on the thickness (40–100 nm), temperature of heating and the Fe:V molar ratio (1:2, 1:1). During the first 300 cycles the cycling stability of the Fe-containing films is better than that of V2O5 crystalline films. UV-visible spectra of charged/discharged films revealed that these films, similar to V2O5 films, exhibit a mixed anodic/cathodic electrochromism. It was established that with regard to the colouring/bleaching changes of V2O5 crystalline films, the Fe/V-oxide films exhibit smaller cathodic colouring at wavelengths λ>600 nm and higher visible transmittance. IR spectroscopy of charged/discharged Fe/V-oxide films confirmed that the reduction of Fe3+ prevents the overreduction of V5+ to V3+, which takes place in V2O5 films cycled in the same potential range.  相似文献   

17.
Sm0.5Sr0.5CoO3 (SSC)-Sm0.2Ce0.8O1.9 (SDC) core-shell composite cathodes are synthesized via a polymerizable complex method, and the durability of a cell incorporating the cathodes is examined. Nanocrystalline SSC powders have been coated onto the surfaces of SDC cores to enable the formation of a rigid backbone structure, over which the catalyst phase is effectively dispersed. A symmetrical SSC-SDC |SDC| SSC-SDC half-cell exhibits a polarization resistance of 0.098 Ω cm2 at 650 °C. The durability and microstructure of the cathode are investigated by electrochemical impedance spectroscopy and thermo-cycle tests at temperatures in the range of 100 °C-650 °C. After 30 cycles, the polarization resistance is found to increase by 9.04 × 10−2 Ω cm2, a 3.56% rise with respect to the initial resistance. Coarsening of the SSC catalyst phase has been prevented with the use of core-shell type powders, as confirmed by a nearly constant low frequency polarization resistance and a microstructural analysis. The performance of a unit cell comprised of the core-shell type cathode exhibits 1.07 W cm−2 at 600 °C and 0.62 W cm−2 at 550 °C.  相似文献   

18.
Layered Li(Ni2/3Mn1/3)O2 compounds are prepared by freeze-drying, mixed carbonate and molten salt methods at high temperature. The phases are characterized by X-ray diffraction, Rietveld refinement, and other methods. Electrochemical properties are studied versus Li-metal by charge–discharge cycling and cyclic voltammetry (CV). The compound prepared by the carbonate route shows a stable capacity of 145 (±3) mAh g−1 up to 100 cycles in the range 2.5–4.3 V at 22 mA g−1. In the range 2.5–4.4 V at 22 mA g−1, the compound prepared by molten salt method has a stable capacity of 135 (±3) mAh g−1 up to 50 cycles and retains 96% of this value after 100 cycles. Capacity-fading is observed in all the compounds when cycled in the range 2.5–4.5 V. All the compounds display a clear redox process at 3.65–4.0 V that corresponds to the Ni2+/3+–Ni3+/4+ couple.  相似文献   

19.
In this work, poly(methyl methacrylate) (PMMA), a non-surfactant polymer was used to synthesize nonstoichiometric Li0.82Ni0.52Mn1.52O4−δ (0 ≤ δ ≤ 0.25) spinels. The presence of the polymer was found to be beneficial with a view to facilitating the use of the spinel in electrodes for lithium batteries. Thus, PMMA allowed spinel particles of a high crystallinity and uniform size and shape to be obtained, and particle size to be tailored by using an appropriate calcining temperature and time. By controlling these variables, spinels in nanometric, submicrometric and micrometric particle sizes were prepared and characterized by chemical analysis, X-ray diffraction, electron microscopy, thermogravimetry and nitrogen adsorptions measurements. The spinels were obtained as highly crystalline phases with lithium and oxygen deficiency and some cation disorder as revealed by chemical analysis, thermogravimetric and XRD data. Their electrochemical performance in two-electrode cells was tested at room temperature and 50 °C over a wide range of charge/discharge rates (from C/4 to 4C). Cell performance was found to depend on particle size rather than on structural properties. Thus, the spinel best performing at 50 °C was that consisting of submicrometric particles, which delivered a high capacity and exhibited the best capacity retention and rate capability. Particles of submicronic size share the advantages of nanometric particles (viz. the ability to withstand high charge/discharge rates) and micrometric particles (a high capacity and stability at low rates).  相似文献   

20.
A cobalt-free composite Sm0.5Sr0.5Fe0.8Cu0.2O3−δ-Ce0.8Sm0.2O2−δ (SSFCu-SDC) is investigated as a cathode for proton-conducting solid oxide fuel cells (H-SOFCs) in intermediate temperature range, with BaZr0.1Ce0.7Y0.1Yb0.1O3−δ (BZCYYb) as the electrolyte. The XRD results show that SSFCu is chemically compatible with SDC at temperatures up to 1100 °C. The quad-layer single cells of NiO-BZCYYb/NiO-BZCYYb/BZCYYb/SSFCu-SDC are operated from 500 to 700 °C with humidified hydrogen (∼3% H2O) as fuel and the static air as oxidant. It shows an excellent power density of 505 mW cm−2 at 700 °C. Moreover, a low electrode polarization resistance of 0.138 Ω cm2 is achieved at 700 °C. Preliminary results demonstrate that the cobalt-free SSFCu-SDC composite is a promising cathode material for H-SOFCs.  相似文献   

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