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1.
Nanocrystalline La1‐xSrxCoO3‐δ (LSC) thin films with a nominal Sr‐content of x = 0.4 were deposited on Ce0.9Gd0.1O1.95 electrolyte substrates using a low temperature sol‐gel process. The structural and chemical properties of the LSC thin films were studied after thermal treatment, which included a calcination step and a variable, extended annealing time at 700 °C or 800 °C. Transmission electron microscopy combined with selected‐area electron diffraction, energy‐dispersive X‐ray spectrometry, and scanning transmission electron microscopy tomography was applied for the investigation of grain size, porosity, microstructure, and analysis of the local chemical composition and element distribution on the nanoscale. The area specific resistance (ASR) values of the thin film LSC cathodes, which include the lowest ASR value reported so far (ASRchem = 0.023 Ωcm2 at 600 °C) can be interpreted on the basis of the structural and chemical characterization.  相似文献   

2.
Nanocrystalline La1‐xSrxCoO3‐δ (LSC) thin films with a nominal Sr‐content of x = 0.4 were deposited on Ce0.9Gd0.1O1.95 electrolyte substrates using a low temperature sol‐gel process. The structural and chemical properties of the LSC thin films were studied after thermal treatment, which included a calcination step and a variable, extended annealing time at 700 °C or 800 °C. Transmission electron microscopy combined with selected‐area electron diffraction, energy‐dispersive X‐ray spectrometry, and scanning transmission electron microscopy tomography was applied for the investigation of grain size, porosity, microstructure, and analysis of the local chemical composition and element distribution on the nanoscale. The area specific resistance (ASR) values of the thin film LSC cathodes, which include the lowest ASR value reported so far (ASRchem = 0.023 Ωcm2 at 600 °C) can be interpreted on the basis of the structural and chemical characterization.  相似文献   

3.
Solid‐oxide fuel cells are an attractive energy conversion technology for clean electric power production. To render them more affordable, discovery of new cathode materials with high reactivity to oxygen reduction reaction (ORR) at temperatures below 700 °C is needed. Recent studies have demonstrated that La0.8Sr0.2CoO3/(La0.5Sr0.5)2CoO4 (LSC113/214) hetero‐interfaces exhibit orders of magnitude faster ORR kinetics compared with either single phase at 500 °C. To obtain a microscopic level understanding and control of such unusual enhancement, we implemented a novel combination of in situ scanning tunneling spectroscopy and focused ion beam milling to probe the local electronic structure at nanometer resolution in model multilayer superlattices. At 200–300 °C, the LSC214 layers are electronically activated through an interfacial coupling with LSC113. Such electronic activation is expected to facilitate charge transfer to oxygen, and concurrent with the anisotropically fast oxygen incorporation on LSC214, quantitatively explains the vastly accelerated ORR kinetics near the LSC113/214 interface. Our results contribute to an improved understanding of oxide hetero‐interfaces at elevated temperatures and identify electronically coupled oxide structures as the basis of novel cathodes with exceptional performance.  相似文献   

4.
Partially amorphous La0.6Sr0.4CoO3‐δ (LSC) thin‐film cathodes are fabricated using pulsed laser deposition and are integrated in free‐standing micro‐solid oxide fuel cells (micro‐SOFC) with a 3YSZ electrolyte and a Pt anode. A low degree of crystallinity of the LSC layers is achieved by taking advantage of the miniaturization of the cells, which permits low‐temperature operation (300–450 °C). Thermomechanically stable micro‐SOFC are obtained with strongly buckled electrolyte membranes. The nanoporous columnar microstructure of the LSC layers provides a large surface area for oxygen incorporation and is also believed to reduce the amount of stress at the cathode/electrolyte interface. With a high rate of failure‐free micro‐SOFC membranes, it is possible to avoid gas cross‐over and open‐circuit voltages of 1.06 V are attained. First power densities as high as 200–262 mW cm?2 at 400–450 °C are achieved. The area‐specific resistance of the oxygen reduction reaction is lower than 0.3 Ω cm2 at 400 °C around the peak power density. These outstanding findings demonstrate that partially amorphous oxides are promising electrode candidates for the next‐generation of solid oxide fuel cells working at low‐temperatures.  相似文献   

5.
Although the Li‐excess layered‐oxide Li2MnO3 has a high theoretical capacity, structural transformations within the oxide during electrochemical cycling lead to relatively low experimental capacities, hindering its use in practical applications. Here, aberration‐corrected scanning transmission electron microscopy/electron energy loss spectroscopy and high‐resolution X‐ray diffraction are used to characterize the oxide following electrochemical cycling. Microscopy reveals the coexistence of regions with local monoclinic, spinel, and rock‐salt symmetries, indicating localized and inhomogeneous structural evolutions. Crystal structure transformations are observed both at the particle surface and in the bulk. At the surface, these transformed regions resemble spinel Mn3O4 or rock‐salt MnO, consistent with oxygen loss. In the bulk, the regions resemble defect spinels, such as the layered‐spinel LixMn4/3O4, which suggest a partial phase transformation consistent with oxygen retention. Both microscopy and diffraction data of the cycled sample indicate areas of pristine Li2MnO3; the presence of such areas, in close proximity to LixMn4/3O4 areas, suggests that the layered to spinel structure transformation is partially reversible. Spinel, disordered rock salt, and pristine areas are also observed in Li2MnO3 samples intentionally damaged by electron beam irradiation. This observation indicates that the dynamic processes resulting in phase transformations can be studied for a variety of oxide systems by a judicious selection of irradiation conditions.  相似文献   

6.
Atomically thin 2D heterostructures have opened new realms in electronic and optoelectronic devices. Herein, 2D lateral heterostructures of mesoporous In2O3–x/In2S3 atomic layers are synthesized through the in situ oxidation of In2S3 atomic layers by an oxygen plasma‐induced strategy. Based on experimental observations and theoretical calculations, the prolonged charge carrier lifetime and increased electron density reveal the efficient photoexcited carrier transport and separation in the In2O3–x/In2S3 layers by interfacial bonding at the atomic level. As expected, the synergistic structural and electronic modulations of the In2O3–x/In2S3 layers generate a photocurrent of 1.28 mA cm?2 at 1.23 V versus a reversible hydrogen electrode, nearly 21 and 79 times higher than those of the In2S3 atomic layers and bulk counterpart, respectively. Due to the large surface area, abundant active sites, broadband‐light harvesting ability, and effective charge transport pathways, the In2O3–x/In2S3 layers build efficient pathways for photoexcited charge in the 2D semiconductive channels, expediting charge transport and kinetic processes and enhancing the robust broadband‐light photo‐electrochemical water splitting performance. This work paves new avenues for the exploration and design of atomically thin 2D lateral heterostructures toward robust photo‐electrochemical applications and solar energy utilization.  相似文献   

7.
Layered lithium–nickel–cobalt–manganese oxide (NCM) materials have emerged as promising alternative cathode materials owing to their high energy density and electrochemical stability. Although high reversible capacity has been achieved for Ni‐rich NCM materials when charged beyond 4.2 V versus Li+/Li, full lithium utilization is hindered by the pronounced structural degradation and electrolyte decomposition. Herein, the unexpected realization of sustained working voltage as well as improved electrochemical performance upon electrochemical cycling at a high operating voltage of 4.9 V in the Ni‐rich NCM LiNi0.895Co0.085Mn0.02O2 is presented. The improved electrochemical performance at a high working voltage at 4.9 V is attributed to the removal of the resistive Ni2+O rock‐salt surface layer, which stabilizes the voltage profile and improves retention of the energy density during electrochemical cycling. The manifestation of the layered Ni2+O rock‐salt phase along with the structural evolution related to the metal dissolution are probed using in situ X‐ray diffraction, neutron diffraction, transmission electron microscopy, and X‐ray absorption spectroscopy. The findings help unravel the structural complexities associated with high working voltages and offer insight for the design of advanced battery materials, enabling the realization of fully reversible lithium extraction in Ni‐rich NCM materials.  相似文献   

8.
Perovskites are promising oxygen carriers for solar‐driven thermochemical fuel production due to higher oxygen exchange capacity. Despite their higher fuel yield capacity, La0.6Sr0.4MnO3 perovskite materials present slow CO2‐splitting kinetics compared with state‐of‐the‐art CeO2. In order to improve the CO production rates, the incorporation of Cr in La0.6Sr0.4MnO3 is explored based on thermodynamic calculations that suggest an enhanced driving force toward CO2 splitting at high temperatures for La0.6Sr0.4CrxMn1?xO3 perovskites. Here, reported is a threefold faster CO fuel production for La0.6Sr0.4Cr0.85Mn0.15O3 compared to conventional La0.6Sr0.4MnO3, and twofold faster than CeO2 under isothermal redox cycling at 1400 °C, and high stability upon long‐term cycling without any evidence of microstructural degradation. The findings suggest that with the proper design in terms of transition metal ion doping, it is possible to adjust perovskite compositions and reactor conditions for improved solar‐to‐fuel thermochemical production under nonconventional solar‐driven thermochemical cycling schemes such as the here presented near isothermal operation.  相似文献   

9.
Li and Mn‐rich layered oxides, xLi2MnO3·(1–x)LiMO2 (M=Ni, Mn, Co), are promising cathode materials for Li‐ion batteries because of their high specific capacity that can exceed 250 mA h g?1. However, these materials suffer from high 1st cycle irreversible capacity, gradual capacity fading, low rate capability, a substantial charge‐discharge voltage hysteresis, and a large average discharge voltage decay during cycling. The latter detrimental phenomenon is ascribed to irreversible structural transformations upon cycling of these cathodes related to potentials ≥4.5 V required for their charging. Transition metal inactivation along with impedance increase and partial layered‐to‐spinel transformation during cycling are possible reasons for the detrimental voltage fade. Doping of Li, Mn‐rich materials by Na, Mg, Al, Fe, Co, Ru, etc. is useful for stabilizing capacity and mitigating the discharge‐voltage decay of xLi2MnO3·(1–x)LiMO2 electrodes. Surface modifications by thin coatings of Al2O3, V2O5, AlF3, AlPO4, etc. or by gas treatment (for instance, by NH3) can also enhance voltage and capacity stability during cycling. This paper describes the recent literature results and ongoing efforts from our groups to improve the performance of Li, Mn‐rich materials. Focus is also on preparation of cobalt‐free cathodes, which are integrated layered‐spinel materials with high reversible capacity and stable performance.  相似文献   

10.
In order to improve the luminescent performance of silicate blue phosphors, Sr(1.5‐x)‐(1.5y)Mg0.5SiO4:xEu2+,yCe3+ phosphors were synthesized using one‐step calcination of a precursor prepared by chemical co‐precipitation. The crystal structure and luminescent properties of the phosphors were analyzed using X‐ray diffraction and fluorescence spectrophotometry, respectively. Because the activated ions (Eu2+) can occupy two different types of sites (Sr1 and Sr2), the emission spectrum of Eu2+ excited at 350 nm contains two single bands (EM1 and EM2) in the wavelength range 400–550 nm, centered at 463 nm, and the emission intensity first increases and then decreases with increasing concentrations of Eu2+ ions. Co‐doping of Ce3+ ions can greatly enhance the emission intensity of Eu2+ by transferring its excitation energy to Eu2+. Because of concentration quenching, a higher substitution concentration of Ce3+ can lead to a decrease in the intensity. Meanwhile, the quantum efficiency of the phosphor is improved after doping with Ce3+, and a blue shift phenomenon is observed in the CIE chromaticity diagram. The results indicate that Sr(1.5‐x)‐(1.5y)Mg0.5SiO4:xEu2+,yCe3+ can be used as a potential new blue phosphor for white light‐emitting diodes.  相似文献   

11.
Various additives to Ni–Fe systems are studied as cermet cathodes for CO2 electrolysis (973–1173 K) using a La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM) electrolyte, which is one of the most promising oxide‐ion conductors for intermediate‐temperature solid‐oxide electrolysis cells in terms of ionic‐transport number and conductivity. It is found that Ni–Fe–La0.6Sr0.4Fe0.8Mn0.2O3 (Ni–Fe–LSFM) exhibits a remarkable performance with a current density of 2.32 A cm?2 at 1.6 V and 1073 K. The cathodic overpotential is significantly decreased by mixing the LSFM powder with Ni–Fe, which is related to the increase in the number of reaction sites for CO2 reduction. For Ni–Fe–LSFM, much smaller particles (<200 nm) are sustained under CO2 electrolysis conditions at high temperatures than for Ni–Fe. X‐ray diffraction analysis suggests that the main phases of Ni–Fe–LSFM are Ni and LaFeO3; thus, the oxide phase of LaFeO3 is also maintained during CO2 electrolysis. Analysis of the gaseous products indicates that only CO is formed, and the rate of CO formation agrees well with that of a four‐electron reduction process, suggesting that the reduction of CO2 to CO proceeds selectively. It is also confirmed that almost no coke is deposited on the Ni–Fe–LSFM cathode after CO2 electrolysis.  相似文献   

12.
The tris(8‐hydroxyquinoline)–aluminium complex is the most important and widely studied as electron transporting and green light emitting material. Alq3 and TbxAl(1‐x)q3 have been synthesized (where x = 0.1, 0.3, 0.5, 0.7 and 0.9) and blended films of Alq3 and TbxAl(1‐x)q3 with PMMA and PS at different percentage weight (wt%) concentrations (e.g., 0.1, 1, 5, 10, 25 and 50 wt%) have been prepared. The synthesized materials and their blended thin films have been characterized by a photoluminescence (PL) technique; the synthesis and PL characterization are reported in this paper. The synthesized metal complex shows bright emission of green light with blue light excitation (440 nm) and the prepared TbxAl(1‐x)q3 phosphor may be applicable in blue chip‐excited OLEDs for the newly developed wallpaper lighting technology. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

13.
In this study, Eu‐doped Li2(Ba1‐xSrx)SiO4 powders (x = 0, 0.2, 0.4, and 0.6) were synthesized at 850°C in a reduction atmosphere (5% H2 + 95% N2) for a duration of 1 h using a solid‐state reaction method. The reduction atmosphere was infused as the synthesis temperature reached 850°C, and was removed as the temperature dropped to 800–500°C. Li2(Ba1‐xSrx)SiO4 (or Li2BaSiO4), (Ba,Sr)2SiO4 (or BaSiO4), and Li4SiO4 phases co‐existed in the synthesized Eu‐doped Li2(Ba1‐xSrx)SiO4 powders. A new finding was that the reduction atmosphere removing (RAR) temperature of the Li2(Ba1‐xSrx)SiO4 phosphors had a large effect on their photoluminescence excitation (PLE) and PL properties. Except for the 800°C‐RAR‐treated Li2BaSiO4 phosphor, PLE spectra of all other Li2(Ba1‐xSrx)SiO4 phosphors had one broad emission band with two emission peaks centred at ~242 and ~283 nm; these PL spectra had one broad emission band with one emission peak centred at 502–514 nm. We showed that the 800°C‐RAR‐treated Li2BaSiO4 phosphor emitted a red light and all other Li2(Ba1‐xSrx)SiO4 phosphors emitted a green light. Reasons for these results are discussed thoroughly.  相似文献   

14.
Developing multielectron reaction electrode materials is essential for achieving high specific capacity and high energy density in secondary batteries; however, it remains a great challenge. Herein, Na3MnTi(PO4)3/C hollow microspheres with an open and stable NASICON framework are synthesized by a spray‐drying‐assisted process. When applied as a cathode material for sodium‐ion batteries, the resultant Na3MnTi(PO4)3/C microspheres demonstrate fully reversible three‐electron redox reactions, corresponding to the Ti3+/4+ (≈2.1 V), Mn2+/3+ (≈3.5 V), and Mn3+/4+ (≈4.0 V vs Na+/Na) redox couples. In situ X‐ray diffraction results reveals that both solid‐solution and two‐phase electrochemical reactions are involved in the sodiation/desodiation processes. The high specific capacity (160 mAh g?1 at 0.2 C), outstanding cyclability (≈92% capacity retention after 500 cycles at 2 C), and the facile synthesis make the Na3MnTi(PO4)3/C a prospective cathode material for sodium‐ion batteries.  相似文献   

15.
A unique approach for the synthesis of nonstoichiometric, mesoporous molybdenum oxide (MoO3–x) with nanosized crystalline walls by using a soft template (PEO‐b‐PS) synthesis method is introduced. The as‐synthesized mesoporous MoO3–x is very active and stable (durability > 12 h) for the electrochemical hydrogen evolution reaction (HER) under both acidic and alkaline conditions. The intrinsic MoO3 serves as an HER electrocatalyst without the assistance of carbon materials, noble metals, or MoS2 materials. The results from transmission electron microscopy and N2 sorption techniques show that the as‐synthesized mesoporous MoO3–x has large accessible pores (20–40 nm), which are able to facilitate mass transport and charge transfer during HER. In terms of X‐ray diffraction, X‐ray photoelectron spectroscopy, temperature‐programmed oxidation, and diffusive reflectance UV–vis spectroscopy, the mesoporous MoO3–x exhibits mixed oxidation states (Mo5+, Mo6+) and an oxygen‐deficient structure. The as‐synthesized MoO3–x only requires a low overpotential (≈0.14 V) to achieve a 10 mA cm?2 current density in 0.1 m KOH and the Tafel slope is as low as 56 mV dec?1. Density functional theory calculations demonstrate a change of electronic structure and the possible reaction pathway of HER. Oxygen vacancies and mesoporosity serve as key factors for excellent performance.  相似文献   

16.
Mechanochemical synthesis of Cu3P in the presence of n‐dodecane results in a material with a secondary particle size distribution of 10 μm, secondary particles which consist of homogeneously agglomerated 20 nm primary particles. The electrochemical performance of Cu3P with lithium is influenced by the reaction depth, in other words by the lower potential cut‐off. During the electrochemical reaction, the displacement of copper by lithium from the Cu3P structure until the formation of Li3P and Cu deteriorates the capacity retention. Improved performance was obtained when the charge potential was limited to 0.50 V (vs. Li/Li+) and the formation of the LixCu3‐xP phase (0 ≤ × ≤ 2). In this case, when the potential is limited to 0.5 V, the capacity is stable for more than 50 cycles. Acceptable electrochemical performances in Li‐ion cells within the voltage range 0.50–2.0 V (vs. Li/Li+) were shown when Cu3P was used as an anode and Li1.2(Ni0.13Mn0.54Co0.13)O2 and LiNi0.5Mn1.5O4 as positive electrode materials.  相似文献   

17.
To achieve the energy‐effective ammonia (NH3) production via the ambient‐condition electrochemical N2 reduction reaction (NRR), it is vital to ingeniously design an efficient electrocatalyst assembling the features of abundant surface deficiency, good dispersibility, high conductivity, and large surface specific area (SSA) via a simple way. Inspired by the fact that the MXene contains thermodynamically metastable marginal transition metal atoms, the oxygen‐vacancy‐rich TiO2 nanoparticles (NPs) in situ grown on the Ti3C2Tx nanosheets (TiO2/Ti3C2Tx) are prepared via a one‐step ethanol‐thermal treatment of the Ti3C2Tx MXene. The oxygen vacancies act as the main active sites for the NH3 synthesis. The highly conductive interior untreated Ti3C2Tx nanosheets could not only facilitate the electron transport but also avoid the self‐aggregation of the TiO2 NPs. Meanwhile, the TiO2 NPs generation could enhance the SSA of the Ti3C2Tx in return. Accordingly, the as‐prepared electrocatalyst exhibits an NH3 yield of 32.17 µg h?1 mg?1cat. at ?0.55 V versus reversible hydrogen electrode (RHE) and a remarkable Faradaic efficiency of 16.07% at ?0.45 V versus RHE in 0.1 m HCl, placing it as one of the most promising NRR electrocatalysts. Moreover, the density functional theory calculations confirm the lowest NRR energy barrier (0.40 eV) of TiO2 (101)/Ti3C2Tx compared with Ti3C2Tx or TiO2 (101) alone.  相似文献   

18.
The novel red‐emitting phosphors KxSr1?2xMoO4:Pr3+x (0.00 ≤ x ≤ 0.04) were prepared by solid‐state reaction. The crystallization and particle sizes of samples were investigated by powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). TEM images were in good agreement with the theoretical calculation data from the XRD patterns. Photoluminescence analysis indicated that there were three excitation peaks under 430–500 nm, and all samples showed the intensely red emission at 648 nm corresponding to the 3P03F2 transition of Pr3+. The concentrations of doping ions, temperature and polyethylene glycol in the phosphor system can significantly influence the intensity of the red emission. The photoluminescence spectral intensity reached its maximum at x = 0.02. The results showed that the investigated phosphor is a potential red phosphor for white light‐emitting diodes. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

19.
LiFe1?yMnyPO4/C nanofiber composites are applied as cathode materials in Li‐ion batteries and their electrochemical properties are explored. Nanofiber meshes are synthesized via electrospinning of commercially available precursors (LiOH·H2O, FeSO4·7H2O, MnSO4·H2O, H3PO4, and polyvinylpyrrolidone). Nanofibers calcined at 850 °C under Ar/H2 (95/5 vol%) atmosphere are directly used as self‐supporting electrodes in Swagelok half cells without the need for any conductive additive or polymer binder. The morphology, phase, and chemical composition of as‐prepared and heat‐treated samples are analyzed by means of X‐ray powder diffraction, thermogravimetric analysis, and electron and scanning microscopy techniques. Brunauer–Emmett–Teller gas adsorption–desorption measurements show a high specific surface area (111m2 g?1) for LiFe0.5Mn0.5PO4. The influence of different Fe/Mn ratios on the morphology, electrical, and electrochemical performances are analyzed.  相似文献   

20.
Ru Liu  Xigui Wang 《Luminescence》2020,35(1):114-119
Eu3+‐doped 6LaPO4–3La3PO7–2La7P3O18 red luminescent phosphors were synthesized by co‐deposition and high‐temperature solid‐state methods and its polyphase state was confirmed by X‐ray diffraction analysis. Transmission electron microscopy showed the grain morphology as a mixture of rods and spheres. Luminescence properties of the phosphor were investigated and its red emission parameters were evaluated as a function of Eu3+ concentration (3.00–6.00 mol%). Excitation spectra of 6LaPO4–3La3PO7–2La7P3O18:Eu3+ showed strong absorption bands at 280, 395, and 466 nm, while the luminescence spectra exhibited prominent red emission peak centred at 615 nm (5D07F2) in the red region. CIE chromaticity coordinates of the 6LaPO4–3La3PO7–2La7P3O18:5%Eu3+ phosphor were (0.668, 0.313) in the red region, and defined its potential application as a red phosphor.  相似文献   

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