首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
A novel double perovskite Sr2FeMo2/3Mg1/3O6?δ is prepared and characterized as an anode material for solid oxide fuel cells (SOFCs). X‐ray diffraction refinement reveals that Mg and Mo cations locate separately in two different B sites (B and B′ in A2BB′O6) while Fe occupies both B and B′ sites, forming the lattice structure with the form of Sr2(Mg1/3Fe2/3)(Mo2/3Fe1/3)O6?δ. The inactive element Mg doping not only endows the material with excellent redox structural stability but also triggers the creation of antisite defects in the crystal lattice, which provide the material with excellent electrochemical activity. The anode performance of Sr2FeMo2/3Mg1/3O6?δ is characterized in an La0.8Sr0.2Ga0.8Mg0.2O3?δ electrolyte supported cell with La0.58Sr0.4Fe0.8Co0.2O3?δ cathode. A peak power density of 531, 803, 1038, and 1316 mW cm?2 at 750, 800, 850, and 900 °C, respectively, is achieved in humidified H2. The Sr2FeMo2/3Mg1/3O6?δ shows suitable thermal expansion coefficient (16.9(2) × 10?6 K?1), high electrical conductivity, and good tolerance to carbon deposition and sulfur poisoning. First‐principle computations demonstrate that the presence of FeB? O? FeB′ bonds can promote the easy formation and fast migration of oxygen vacancies in the lattice, which are the key to affecting the anode reaction kinetics. The excellent overall performance of Sr2FeMo2/3Mg1/3O6?δ compound makes it a promising anode material for SOFCs.  相似文献   

2.
The oxygen evolution reaction (OER) is of prime importance in multiple energy storage devices. Perovskite oxides involving lattice‐oxygen oxidation are generally regarded as highly active OER catalysts, but the deprotonation of surface‐bound intermediates limit the further activity improvement. Here, it is shown that this kinetic limitation can be removed by introducing Sr3B2O6 (SB) which activates a proton‐acceptor functionality to boost OER activity. As a proof‐of‐concept example, an experimental validation is conducted on the extraordinary OER performance of a Sr(Co0.8Fe0.2)0.7B0.3O3?δ (SCFB‐0.3) hybrid catalyst, made using Sr0.8Co0.8Fe0.2O3?δ as active component and SB as a proton acceptor. This smart hybrid exhibits an exceptionally ultrahigh OER activity with an extremely low overpotential of 340 mV in 0.1 m KOH and 240 mV in 1 m KOH required for 10 mA cm?2 which is the top‐level catalytic activity among metal oxides reported so far, while maintaining excellent durability. The correlation of pH and activity study reveals that this enhanced activity mainly originates from the improved interfacial proton transfer. Such a strategy further demonstrated to be universal, which can be applied to enhance the OER activity of other high covalent oxides with close O 2p‐band centers relative to Fermi energy.  相似文献   

3.
Two series of red‐emitting phosphors Sr‐Ba‐Mo‐W‐O:Eu,Sm and Sr‐Ba‐Mo‐W‐O:Eu have been synthesized by a sol–gel method. The effects of the chemical composition, concentrations of Sm3+ and Eu3+, the Sr2+/Ba2+ ratio, and the W6+/Mo6+ ratio on the luminescent properties were investigated. The as‐prepared phosphors were characterized by X‐ray diffraction and Raman spectra. Results showed that single phases of the two series were prepared. The compositions of Sr0.6Ba0.13Mo0.8 W0.2O4:Eu0.10Sm0.08 and Sr0.75Ba0.1Mo0.8 W0.2O4:Eu0.10 had the strongest luminescent intensity. The excitation spectra of Sm3+, Eu3+ co‐doped phosphors were broader and the strongest peak moved to 404 nm when compared with that of Eu3+ single‐doped phosphors. The luminescent intensity of the Sr0.6Ba0.13Mo0.8 W0.2O4:Eu0.10Sm0.08 at 618 nm were 2.8 times greater than that of Sr0.75Ba0.1Mo0.8 W0.2O4:Eu0.10. The luminescent intensity of Sr0.6Ba0.13Mo0.8 W0.2O4:Eu0.10Sm0.08 and Sr0.75Ba0.1Mo0.8 W0.2O4:Eu0.10 at 150 °C decreased to 56.8% and 50.3% of the initial value at room temperature, respectively. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

4.
Overcoming the sluggish activity of cathode materials is critical to realizing the wide‐spread application of intermediate‐temperature solid oxide fuel cells. Herein, a new way is reported to tune the performance of perovskite‐type materials as oxygen reduction electrodes by embedding anions (F?) in oxygen sites. The obtained perovskite oxyfluorides SrFeO3?σ ?δ Fσ and SrFe0.9Ti0.1O3?σ ?δ Fσ (σ = 0.05 and 0.10) show improved electrocatalytic activity compared to their parent oxides, achieving area specific resistance values of 0.875, 0.393, and 0.491 Ω cm2 for SrFeO3?δ , SrFeO2.95?δ F0.05, and SrFeO2.90?δ F0.10, respectively, at 600 °C in air. Such improved performance is a result of the improved bulk diffusion and surface exchange properties due to anion doping. Moreover, favorable stability in performance is also demonstrated for the F? anion‐doped perovskites as oxygen reduction electrodes at 650 °C for a test period of ≈200 h. A combination of anion doping and cation doping may provide a highly attractive strategy for the future development of cathode materials.  相似文献   

5.
The oxygen isotope signature of sulphate (δ18Osulphate) is increasingly used to study nutritional fluxes and sulphur transformation processes in a variety of natural environments. However, mechanisms controlling the δ18Osulphate signature in soil–plant systems are largely unknown. The objective of this study was to determine key factors, which affect δ18Osulphate values in soil and plants. The impact of an 18O‐water isotopic gradient and different types of fertilizers was investigated in a soil incubation study and a radish (Raphanus sativus L.) greenhouse growth experiment. Water provided 31–64% of oxygen atoms in soil sulphate formed via mineralization of organic residues (green and chicken manures) while 49% of oxygen atoms were derived from water during oxidation of elemental sulphur. In contrast, δ18Osulphate values of synthetic fertilizer were not affected by soil water. Correlations between soil and plant δ18Osulphate values were controlled by water δ18O values and fertilizer treatments. Additionally, plant δ34S data showed that the sulphate isotopic composition of plants is a function of S assimilation. This study documents the potential of using compound‐specific isotope ratio analysis for investigating and tracing fertilization strategies in agricultural and environmental studies.  相似文献   

6.
Li‐rich layered oxides (LLOs) can deliver almost double the capacity of conventional electrode materials such as LiCoO2 and LiMn2O4; however, voltage fade and capacity degradation are major obstacles to the practical implementation of LLOs in high‐energy lithium‐ion batteries. Herein, hexagonal La0.8Sr0.2MnO3?y (LSM) is used as a protective and phase‐compatible surface layer to stabilize the Li‐rich layered Li1.2Ni0.13Co0.13Mn0.54O2 (LM) cathode material. The LSM is Mn? O? M bonded at the LSM/LM interface and functions by preventing the migration of metal ions in the LM associated with capacity degradation as well as enhancing the electrical transfer and ionic conductivity at the interface. The LSM‐coated LM delivers an enhanced reversible capacity of 202 mAh g?1 at 1 C (260 mA g?1) with excellent cycling stability and rate capability (94% capacity retention after 200 cycles and 144 mAh g?1 at 5 C). This work demonstrates that interfacial bonding between coating and bulk material is a successful strategy for the modification of LLO electrodes for the next‐generation of high‐energy Li‐ion batteries.  相似文献   

7.
A series of Sr1‐x‐yCayMoO4:xSm3+ (0 ≤ x ≤ 7 mol% and 0 ≤ y < 1) phosphors was synthesized by a conventional solid‐state reaction method in air, and their structural and spectroscopic properties were investigated. The optimal doping concentration of Sm3+ in SrMoO4:Sm3+ phosphor is 5 mol%. Under excitation with 275 nm, in Sr1‐x‐yCayMoO4:xSm3+ (0 ≤ x ≤ 7 mol% and 0 ≤ y < 1) phosphors, the emission band of the host was found to overlap with the excitation bands peaking at ~500 nm of Sm3+ ion, and the energy transfer from MoO42? group to Sm3+ ion can also be observed. The International Commission on Illumination (CIE) chromaticity coordinates of Sr0.95‐yCayMoO4:0.05Sm3+ phosphors with excitation 275 nm varied systematically from an orange (0.4961, 0.3761) (y = 0) to a white color (0.33, 0.3442) (y = 0.95) with increasing calcium oxide (CaO) concentration. However, Sr0.95‐yCayMoO4:0.05Sm3+ phosphors with excitation at 404 nm only showed red emission and the energy transfer between MoO42? group to Sm3+ ion was not observed. The complex mechanisms of luminescence and energy transfer are discussed by energy level diagrams of MoO42? group and Sm3+ ion. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

8.
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   

9.
Doped perovskite oxides with the general formula of AxA′1?xByB′1?yO3 have been extensively exploited as the cathode materials of solid oxide fuel cells (SOFCs), but the performance at low‐to‐medium temperatures still needs improvement. BaCo0.4Fe0.4Zr0.1Y0.1O3?δ (BCFZY) has been recently reported to show promising oxygen reduction reaction (ORR) activity under SOFCs' operating conditions. Here, it is reported that the activity of BCFZY can be further boosted via introducing a slight B‐site cation deficiency into the oxide lattice, and such an improvement is assigned to an increase in oxygen mobility that brings enhancement in both surface exchange and bulk diffusion kinetics. Specifically, materials with the nominal composition of Ba(Co0.4Fe0.4Zr0.1Y0.1)0.975O3?δ and Ba(Co0.4Fe0.4Zr0.1Y0.1)0.95O3?δ show significantly improved activity for ORR at reduced temperatures with the area specific resistances of 0.011 and 0.024 Ω cm2 at 600 °C, as a comparison of 0.042 Ω cm2 for the cation stoichiometric BCFZY. Excessive B‐site deficiencies, however, lead to the formation of impurity phases, which cause a block for charge transfer and, consequently, a reduction in electrode performance. Introducing a B‐site cation deficiency is a promising way to optimize the activity of perovskite oxides for ORR at reduced temperatures, but the degree of deficiency shall be carefully tuned.  相似文献   

10.
Ni‐rich Li[NixCoyMn1?x?y]O2 (x ≥ 0.8) layered oxides are the most promising cathode materials for lithium‐ion batteries due to their high reversible capacity of over 200 mAh g?1. Unfortunately, the anisotropic properties associated with the α‐NaFeO2 structured crystal grains result in poor rate capability and insufficient cycle life. To address these issues, a micrometer‐sized Ni‐rich LiNi0.8Co0.1Mn0.1O2 secondary cathode material consisting of radially aligned single‐crystal primary particles is proposed and synthesized. Concomitant with this unique crystallographic texture, all the exposed surfaces are active {010} facets, and 3D Li+ ion diffusion channels penetrate straightforwardly from surface to center, remarkably improving the Li+ diffusion coefficient. Moreover, coordinated charge–discharge volume change upon cycling is achieved by the consistent crystal orientation, significantly alleviating the volume‐change‐induced intergrain stress. Accordingly, this material delivers superior reversible capacity (203.4 mAh g?1 at 3.0–4.3 V) and rate capability (152.7 mAh g?1 at a current density of 1000 mA g?1). Further, this structure demonstrates excellent cycling stability without any degradation after 300 cycles. The anisotropic morphology modulation provides a simple, efficient, and scalable way to boost the performance and applicability of Ni‐rich layered oxide cathode materials.  相似文献   

11.
Previous mangrove tree ring studies attempted, unsuccessfully, to relate the δ18O of trunk cellulose (δ18OCELL) to the δ18O of source water (δ18OSW). Here, we tested whether biochemical fractionation associated with one of the oxygen in the cellulose glucose moiety or variation in leaf water oxygen isotope fractionation (ΔLW) can interfere with the δ18OSW signal as it is recorded in the δ18OCELL of mangrove (saltwater) and hammock (freshwater) plants. We selected two transects experiencing a salinity gradient, located in the Florida Keys, USA. The δ18OCELL throughout both transects did not show the pattern expected based on that of the δ18OSW. We found that in one of the transects, biochemical fractionation interfered with the δ18OSW signal, while in the other transect ΔLW differed between mangrove and hammock plants. Observed differences in ΔLW between mangroves and hammocks were caused by a longer effective leaf mixing length (L) of the water pathway in mangrove leaves compared to those of hammock leaves. Changes in L could have caused the δ18OCELL to record not only variations in the δ18OSW but also in ΔLW making it impossible to isolate the δ18OSW signal.  相似文献   

12.
LiNixMnyCo1?x?yO2 (NMC) cathode materials with Ni ≥ 0.8 have attracted great interest for high energy‐density lithium‐ion batteries (LIBs) but their practical applications under high charge voltages (e.g., 4.4 V and above) still face significant challenges due to severe capacity fading by the unstable cathode/electrolyte interface. Here, an advanced electrolyte is developed that has a high oxidation potential over 4.9 V and enables NMC811‐based LIBs to achieve excellent cycling stability in 2.5–4.4 V at room temperature and 60 °C, good rate capabilities under fast charging and discharging up to 3C rate (1C = 2.8 mA cm?2), and superior low‐temperature discharge performance down to ?30 °C with a capacity retention of 85.6% at C/5 rate. It is also demonstrated that the electrode/electrolyte interfaces, not the electrolyte conductivity and viscosity, govern the LIB performance. This work sheds light on a very promising strategy to develop new electrolytes for fast‐charging high‐energy LIBs in a wide‐temperature range.  相似文献   

13.
It is shown that an electrochemically‐driven oxide overcoating substantially improves the performance of metal electrodes in high‐temperature electrochemical applications. As a case study, Pt thin films are overcoated with (Pr,Ce)O2?δ (PCO) by means of a cathodic electrochemical deposition process that produces nanostructured oxide layers with a high specific surface area and uniform metal coverage and then the coated films are examined as an O2‐electrode for thin‐film‐based solid oxide fuel cells. The combination of excellent conductivity, reactivity, and durability of PCO dramatically improves the oxygen reduction reaction rate while maintaining the nanoscale architecture of PCO layers and thus the performance of the PCO‐coated Pt thin‐film electrodes at high temperatures. As a result, with an oxide coating step lasting only 5 min, the electrode resistance is successfully reduced by more than 1000 times at 500 °C in air. These observations provide a new direction for the design of high‐performance electrodes for high‐temperature electrochemical cells.  相似文献   

14.
A one‐step, facile supercritical‐ethanol‐fluid synthesis of Se‐modified Ru nanoparticles nucleated on carbon defects is reported, and it is demonstrated that these nanoparticles provide, with >70% efficiency at 1 A g?1, a highly active and reversible oxygen‐reduction/oxygen‐evolution reaction on an air cathode in a nonaqueous electrolyte. The Se modification not only prevents Ru oxidation during charge/discharge cycling, but also improves the catalytic activity by promoting Li2O2 versus Li2O deposited on the Ru particles during discharge. A computational calculation with density functional theory supports the role of a larger electron transfer to the oxygen of Li2O2 adsorbed on a surface layer of RuSe2?δ than on a surface layer of RuO2, thereby shifting the more stable adsorbent from Li2O to Li2O2.  相似文献   

15.
Spatial variation in marine oxygen isotope ratios (δ18O) resulting from differential evaporation rates and precipitation inputs is potentially useful for characterizing marine mammal distributions and tracking movements across δ18O gradients. Dentine hydroxyapatite contains carbonate and phosphate that precipitate in oxygen isotopic equilibrium with body water, which in odontocetes closely tracks the isotopic composition of ambient water. To test whether dentine oxygen isotope composition reliably records that of ambient water and can therefore serve as a proxy for odontocete distribution and movement patterns, we measured δ18O values of dentine structural carbonate (δ18OSC) and phosphate (δ18OP) of seven odontocete species (n = 55 individuals) from regional marine water bodies spanning a surface water δ18O range of several per mil. Mean dentine δ18OSC (range +21.2 to +25.5‰ VSMOW) and δ18OP (+16.7 to +20.3‰) values were strongly correlated with marine surface water δ18O values, with lower dentine δ18OSC and δ18OP values in high‐latitude regions (Arctic and Eastern North Pacific) and higher values in the Gulf of California, Gulf of Mexico, and Mediterranean Sea. Correlations between dentine δ18OSC and δ18OP values with marine surface water δ18O values indicate that sequential δ18O measurements along dentine, which grows incrementally and archives intra‐ and interannual isotopic composition over the lifetime of the animal, would be useful for characterizing residency within and movements among water bodies with strong δ18O gradients, particularly between polar and lower latitudes, or between oceans and marginal basins.  相似文献   

16.
Seasonal variation in δ13C and δ18O of cellulose (δ13Cc and δ18Oc) was measured within two annual rings of Pinus radiata growing at three sites in New Zealand. In general, both δ13Cc and δ18Oc increased to a peak over summer. The three sites differed markedly in annual water balance, and these differences were reflected in δ13Cc and δ18Oc. Average δ13Cc and δ18Oc from each site were positively related, so that the driest site had the most enriched cellulose. δ13Cc and δ18Oc were also related within each site, although both the slope and the closeness of fit of the relationship varied between sites. Supporting the theory, the site with the lowest average relative humidity also had the greatest change in δ18Oc‰ change in δ13Cc. Specific climatic events, such as drought or high rainfall, were recorded as a peak or a trough in enrichment, respectively. These results suggest that seasonal and between‐site variation in δ13Cc and δ18Oc are driven by the interaction between variation in climatic conditions and soil water availability, and plant response to this variation.  相似文献   

17.
A novel tunable red emitting phosphor LiBaB9O15:Sm2+/Sm3+, Li+ with broad excitation band was synthesized by a high temperature solid‐state method. Luminescence properties were investigated in detail by luminescence, X‐ray photoelectron spectroscopy (XPS) spectra and CIE chromaticity coordinates. XPS data confirmed that there were Sm3+ in LiBaB9O15:Sm3+ and Sm2+/Sm3+ in LiBaB9O15:Sm2+/Sm3+, respectively. Spectral property of LiBaB9O15:Sm3+, LiBaB9O15:Sm3+/Sm2+ and LiBaB9O15:Sm2+, Li+ presented that the excitation band of Sm3+ widened and the excitation band of Sm2+ ranged from 350 to 450 nm. And the red light color is tunable with changing Li+ concentration. The results indicated that LiBaB9O15:Sm2+/Sm3+, Li+ may be promising red phosphor for white light emitting diodes.  相似文献   

18.
Using both oxygen isotope ratios of leaf water (δ18OL) and cellulose (δ18OC) of Tillandsia usneoides in situ, this paper examined how short‐ and long‐term responses to environmental variation and model parameterization affected the reconstruction of the atmospheric water vapour (δ18Oa). During sample‐intensive field campaigns, predictions of δ18OL matched observations well using a non‐steady‐state model, but the model required data‐rich parameterization. Predictions from the more easily parameterized maximum enrichment model (δ18OL–M) matched observed δ18OL and observed δ18Oa when leaf water turnover was less than 3.5 d. Using the δ18OL–M model and weekly samples of δ18OL across two growing seasons in Florida, USA, reconstructed δ18Oa was ?12.6 ± 0.3‰. This is compared with δ18Oa of ?12.4 ± 0.2‰ resolved from the growing‐season‐weighted δ18OC. Both of these values were similar to δ18Oa in equilibrium with precipitation, ?12.9‰. δ18Oa was also reconstructed through a large‐scale transect with δ18OL and the growing‐season‐integrated δ18OC across the southeastern United States. There was considerable large‐scale variation, but there was regional, weather‐induced coherence in δ18Oa when using δ18OL. The reconstruction of δ18Oa with δ18OC generally supported the assumption of δ18Oa being in equilibrium with precipitation δ18O (δ18Oppt), but the pool of δ18Oppt with which δ18Oa was in equilibrium – growing season versus annual δ18Oppt – changed with latitude.  相似文献   

19.
The microbial induced calcite precipitation (MICP) has been explored using well-known urease producer bacterium Sporosarcina pasteurii for many applications including soil stabilization. Urease enzyme hydrolyzes urea and in the presence of calcium chloride causes calcium carbonate precipitation between sand particles increasing sand stiffness and strength. In this study, the liquefied soil samples from Anzali coast were positioned inside injection columns by standard positioning technique. The columns were treated by injecting S. pasteurii suspension and cementation solution (CaCl2 and urea). The effect of different conditions consisting of number of injections, injection intervals, flow rate, and ratio of injection solution on unconfined compression strength (USC) of sands formed inside the columns were evaluated. The results indicated that soil strength was increased when ratio of reactant solutions and injection time were elevated. Moreover, the maximum Ca-precipitation in MICP reaction in liquid medium was obtained while Fe3O4/starch concentration and time of addition of nanoparticle to culture medium were 10.8?mg/L and 1.4?h, respectively. The USC results showed that the columns injected by bacterial suspension treated by Fe3O4/starch under optimized conditions improved the soil strength up to 1200?kPa in comparison to the control column as 220?kPa.  相似文献   

20.
Herein, a new P2‐type layered oxide is proposed as an outstanding intercalation cathode material for high energy density sodium‐ion batteries (SIBs). On the basis of the stoichiometry of sodium and transition metals, the P2‐type Na0.55[Ni0.1Fe0.1Mn0.8]O2 cathode is synthesized without impurities phase by partially substituting Ni and Fe into the Mn sites. The partial substitution results in a smoothing of the electrochemical charge/discharge profiles and thus greatly improves the battery performance. The P2‐type Na0.55[Ni0.1Fe0.1Mn0.8]O2 cathode delivers an extremely high discharge capacity of 221.5 mAh g?1 with a high average potential of ≈2.9 V (vs Na/Na+) for SIBs. In addition, the fast Na‐ion transport in the P2‐type Na0.55[Ni0.1Fe0.1Mn0.8]O2 cathode structure enables good power capability with an extremely high current density of 2400 mA g?1 (full charge/discharge in 12 min) and long‐term cycling stability with ≈80% capacity retention after 500 cycles at 600 mA g?1. A combination of electrochemical profiles, in operando synchrotron X‐ray diffraction analysis, and first‐principles calculations are used to understand the overall Na storage mechanism of P2‐type Na0.55[Ni0.1Fe0.1Mn0.8]O2.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号