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1.
On the basis of extreme similarity between the triangle phase diagrams of LiNiO2–LiTiO2–Li[Li1/3Ti2/3]O2 and LiNiO2–LiMnO2–Li[Li1/3Mn2/3]O2, new Li–Ni–Ti–O series with a nominal composition of Li1+z/3Ni1/2−z/2Ti1/2+z/6O2 (0 ≤ z ≤ 0.5) was designed and attempted to prepare via a spray-drying method. XRD identified that new Li–Ni–Ti–O compounds had cubic rocksalt structure, in which Li, Ni and Ti were evenly distributed on the octahedral sites in cubic closely packed lattice of oxygen ions. They can be considered as the solid solution between cubic LiNi1/2Ti1/2O2 and Li[Li1/3Ti2/3]O2 (high temperature form). Charge–discharge tests showed that Li–Ni–Ti–O compounds with appropriate compositions could display a considerable capacity (more than 80 mAh g−1 for 0.2 ≤ z ≤ 0.27) at room temperature in the voltage range of 4.5–2.5 V and good electrochemical properties within respect to capacity (more than 150 mAh g−1 for 0 ≤ z ≤ 0.27), cycleability and rate capability at an elevated temperature of 50 °C. These suggest that the disordered cubic structure in some cases may function as a good host structure for intercalation/deintercalation of Li+. A preliminary electrochemical comparison between Li1+z/3Ni1/2−z/2Ti1/2+z/6O2 (0 ≤ z ≤ 0.5) and Li6/5Ni2/5Ti2/5O2 indicated that charge–discharge mechanism based on Ni redox at the voltage of >3.0 V behaved somewhat differently, that is, Ni could be reduced to +2 in Li1+z/3Ni1/2−z/2Ti1/2+z/6O2 while +3 in Li6/5Ni2/5Ti2/5O2. Reduction of Ti4+ at a plateau of around 2.3 V could be clearly detected in Li1+z/3Ni1/2−z/2Ti1/2+z/6O2 with 0.27 ≤ z ≤ 0.5 at 50 °C after a deep charge associated with charge compensation from oxygen ion during initial cycle.  相似文献   

2.
Laminar burning velocities of CO–H2–CO2–O2 flames were measured by using the outwardly spherical propagating flame method. The effect of large fraction of hydrogen and CO2 on flame radiation, chemical reaction, and intrinsic flame instability were investigated. Results show that the laminar burning velocities of CO–H2–CO2–O2 mixtures increase with the increase of hydrogen fraction and decrease with the increase of CO2 fraction. The effect of hydrogen fraction on laminar burning velocity is weakened with the increase of CO2 fraction. The Davis et al. syngas mechanism can be used to calculate the syngas oxyfuel combustion at low hydrogen and CO2 fraction but needs to be revised and validated by additional experimental data for the high hydrogen and CO2 fraction. The radiation of syngas oxyfuel flame is much stronger than that of syngas–air and hydrocarbons–air flame due to the existence of large amount of CO2 in the flame. The CO2 acts as an inhibitor in the reaction process of syngas oxyfuel combustion due to the competition of the reactions of H + O2 = O + OH, CO + OH = CO2 + H and H + O2(+M) = HO2(+M) on H radical. Flame cellular structure is promoted with the increase of hydrogen fraction and is suppressed with the increase of CO2 fraction due to the combination effect of hydrodynamic and thermal-diffusive instability.  相似文献   

3.
In this work, dehydrogenation and rehydrogenation of three LiNH2/CaH2 samples with LiNH2/CaH2 molar ratio of 2/1, 3/1 and 4/1 were systematically investigated. Remarkable differences were observed in the temperature dependence of hydrogen desorption and subsequent absorption. LiNH2/CaH2 in a molar ratio of 2/1 transforms to ternary imide Li2Ca(NH)2 after desorbing about 4.5 wt.% H2 at 350 °C. And it has a reversible hydrogen storage capacity of 2.7 wt.% at 200 °C. As for the LiNH2/CaH2 mixture in a molar ratio of 4/1, it transforms to a new compound with a composition of Li4CaN4H6 after being dehydrogenated at 350 °C. The rehydrogenation of both LiCa(NH)2 and Li4CaN4H6 gives LiNH2, LiH and the solid solution of 2CaNH–Ca(NH2)2.  相似文献   

4.
Thermal behaviors and stability of glass/glass–ceramic-based sealant materials are critical issues for high temperature solid oxide fuel/electrolyzer cells. To understand the thermophysical properties and devitrification behavior of SrO–La2O3–Al2O3–B2O3–SiO2 system, glasses were synthesized by quenching (25 − X)SrO–20La2O3–(7 + X)Al2O3–40B2O3–8SiO2 oxides, where X was varied from 0.0 mol% to 10.0 mol% at 2.5 mol% interval. Thermal properties were characterized by dilatometry and differential scanning calorimetry (DSC). Microstructural studies were performed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). All the compositions have a glass transition temperature greater than 620 °C and a crystallization temperature greater than 826 °C. Also, all the glasses have a coefficient of thermal expansion (CTE) between 9.0 × 10−6 K−1 and 14.5 × 106 K−1 after the first thermal cycle. La2O3 and B2O3 contribute to glass devitrification by forming crystalline LaBO3. Al2O3 stabilizes the glasses by suppressing devitrification. Significant improvement in devitrification resistance is observed as X increases from 0.0 mol% to 10.0 mol%.  相似文献   

5.
The cermet consisting of electronic conductor Ni and proton conductor La2Ce2O7 (LDC) shows good chemical stability but poor hydrogen permeability. In order to improve the hydrogen permeability, novel Ni–La2−xSmxCe2O7 (x = 0, 0.025, 0.05, 0.075, 0.1 and 0.2) cermets were developed for hydrogen separation. The results show that Sm element doping of LDC can affect the rate of hydrogen permeation, with Ni–La1.95Sm0.05Ce2O7 possessing the highest hydrogen permeation fluxes.  相似文献   

6.
Significant improvements in the hydrogen absorption/desorption properties of the 2LiNH2–1.1MgH2–0.1LiBH4 composite have been achieved by adding 3wt% ZrCo hydride. The composite can absorb 5.3wt% hydrogen under 7.0 MPa hydrogen pressure in 10 min and desorb 3.75wt% hydrogen under 0.1 MPa H2 pressure in 60 min at 150 °C, compared with 2.75wt% and 1.67wt% hydrogen under the same hydrogenation/dehydrogenation conditions without the ZrCo hydride addition, respectively. TPD measurements showed that the dehydrogenation temperature of the ZrCo hydride-doped sample was decreased about 10 °C compared to that of the pristine sample. It is concluded that both the homogeneous distribution of ZrCo particles in the matrix observed by SEM and EDS and the destabilized N–H bonds detected by IR spectrum are the main reasons for the improvement of H-cycling kinetics of the 2LiNH2–1.1MgH2–0.1LiBH4 system.  相似文献   

7.
In situ Raman spectroscopy was used to monitor the dehydrogenation of ball-milled mixtures of LiNH2–LiBH4–MgH2 nanoparticles. The as-milled powders were found to contain a mixture of Li4BN3H10 and Mg(NH2)2, with no evidence of residual LiNH2 or LiBH4. It was observed that the dehydrogenation of both of Li4BN3H10 and Mg(NH2)2 begins at 353 K. The Mg(NH2)2 was completely consumed by 415 K, while Li4BN3H10 persisted and continued to release hydrogen up to 453 K. At higher temperatures Li4BN3H10 melts and reacts with MgH2 to form Li2Mg(NH)2 and hydrogen gas. Cycling studies of the ball-milled mixture at 423 K and 8 MPa (80 bar) found that during rehydrogenation of Li4BN3H10 Raman spectral modes reappear, indicating partial reversal of the Li4BN3H10 to Li2Mg(NH)2 transformation.  相似文献   

8.
9.
In this article, we investigate the ternary LiNH2–MgH2–LiBH4 hydrogen storage system by adopting various processing reaction pathways. The stoichiometric ratio of LiNH2:MgH2:LiBH4 is kept constant with a 2:1:1 molar ratio. All samples are prepared using solid-state mechano-chemical synthesis with a constant rotational speed, but with varying milling duration. Furthermore, the order of addition of parent compounds as well as the crystallite size of MgH2 are varied before milling. All samples are intimate mixtures of Li–B–N–H quaternary hydride phase with MgH2, as evidenced by XRD and FTIR measurements. It is found that the samples with MgH2 crystallite sizes of approximately 10 nm exhibit lower initial hydrogen release at a temperature of 150 °C. Furthermore, it is observed that the crystallite size of Li–B–N–H has a significant effect on the amount of hydrogen release with an optimum size of 28 nm. The as-synthesized hydrides exhibit two main hydrogen release temperatures, one around 160 °C and the other around 300 °C. The main hydrogen release temperature is reduced from 310 °C to 270 °C, while hydrogen is first reversibly released at temperatures as low as 150 °C with a total hydrogen capacity of ∼6 wt.%. Detailed thermal, capacity, structural and microstructural properties are discussed and correlated with the activation energies of these materials.  相似文献   

10.
An Al/conductive coating/α-PbO2–CeO2–TiO2/β-PbO2–MnO2–WC–ZrO2 composite electrode material was prepared through electrochemical oxidation co-deposition on an Al/conductive coating/α-PbO2–CeO2–TiO2 substrate. The effects of manganese nitrate concentration on the chemical composition, electrocatalytic activity, and stability of the composite anode material were investigated using energy dispersive X-ray spectroscopy, anode polarization curves, quasi-stationary polarization curves, electrochemical impedance spectroscopy, scanning electron microscopy, and X-ray diffraction. Results revealed that the WC and nano-ZrO2 content in the β-PbO2–MnO2–WC–ZrO2 composite coatings increased with increasing manganese nitrate concentration. Moreover, the highest values of 6.61 wt% and 3.51 wt%, respectively, were achieved at 80 g L−1 manganese nitrate. PbO2 content decreased and MnO2 content increased with the increasing manganese nitrate concentration; both the descending and ascending trends were nonlinear. The Al/conductive coating/α-PbO2–CeO2–TiO2/β-PbO2–MnO2–WC–ZrO2 composite electrode obtained at 80 g L−1 manganese nitrate concentration in plating solution exhibited reduced overpotential for oxygen evolution (0.610 V at 500 A m−2), highest electrocatalytic activity, longest service life (360 h at 40 °C in 150 g L−1 H2SO4 solution at 2 A cm−2), and lowest cell voltage (2.75 V at 500 A m−2). Furthermore, the composite coating obtained with 80 g L−1 manganese nitrate had uniform crystal grains. The deposit formed was flat, dense, and crackless.  相似文献   

11.
In a previous paper, it was demonstrated that a MgH2–NaAlH4 composite system had improved dehydrogenation performance compared with as-milled pure NaAlH4 and pure MgH2 alone. The purpose of the present study was to investigate the hydrogen storage properties of the MgH2–NaAlH4 composite in the presence of TiF3. 10 wt.% TiF3 was added to the MgH2–NaAlH4 mixture, and its catalytic effects were investigated. The reaction mechanism and the hydrogen storage properties were studied by X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry (DSC), temperature-programmed-desorption and isothermal sorption measurements. The DSC results show that MgH2–NaAlH4 composite milled with 10 wt.% TiF3 had lower dehydrogenation temperatures, by 100, 73, 30, and 25 °C, respectively, for each step in the four-step dehydrogenation process compared to the neat MgH2–NaAlH4 composite. Kinetic desorption results show that the MgH2–NaAlH4–TiF3 composite released about 2.4 wt.% hydrogen within 10 min at 300 °C, while the neat MgH2–NaAlH4 sample only released less than 1.0 wt.% hydrogen under the same conditions. From the Kissinger plot, the apparent activation energy, EA, for the decomposition of MgH2, NaMgH3, and NaH in the MgH2–NaAlH4–TiF3 composite was reduced to 71, 104, and 124 kJ/mol, respectively, compared with 148, 142, and 138 kJ/mol in the neat MgH2–NaAlH4 composite. The high catalytic activity of TiF3 is associated with in situ formation of a microcrystalline intermetallic Ti–Al phase from TiF3 and NaAlH4 during ball milling or the dehydrogenation process. Once formed, the Ti–Al phase acts as a real catalyst in the MgH2–NaAlH4–TiF3 composite system.  相似文献   

12.
To improve the dehydrogenation properties of MgH2, a novel hydrogen storage system, MgH2–Li3AlH6, is prepared by mechanochemical milling. Three physical mixtures containing different mole ratios (1:4, 1:1 and 4:1) of MgH2 and Li3AlH6 are studied and there exists a mutual destabilization effect between the components. The last mixture shows a capacity of 6.5 wt% H2 with the lowest starting temperature of dehydrogenation (170 °C). First, Li3AlH6 decomposes into Al, LiH and H2, and then the as-formed Al can easily destabilize MgH2 to form the intermetallic compound Mg17Al12 at a temperature of 235 °C, which is about 180 °C lower than the decomposition temperature of pristine MgH2. Finally, the residual MgH2 undergoes a self-decomposition whose apparent activation energy has been reduced by about 22 kJ mol−1 compared with pristine MgH2. At a constant temperature of 250 °C, the mixture can dehydrogenate completely under an initial vacuum and rehydrogenate to form MgH2 under 2 MPa H2, showing good cycle stability after the first cycle with a capacity of 4.5 wt% H2. The comparison between 4 MgH2 + Li3AlH6 and 4 MgH2 + LiAlH4 mixtures is also investigated.  相似文献   

13.
NaBH4–NH3BH3 composites were prepared by high-energy ball-milling processes for hydrogen generation through hydrolysis. After ball milling, there were no new phases found in the XRD patterns of NaBH4–NH3BH3 composites. The experimental results demonstrate that when the molar ratios of NaBH4–NH3BH3 composites range from 1:4 to 2:1, these composites can release above 90% hydrogen in 30 min at 70 °C. Comparing with neat NaBH4 or NH3BH3, the hydrolysis properties of these composites are greatly enhanced. And the hydrolysis reaction mechanism is turned out to be more explicit as Na2B4O5(OH)4·8H2O appears in the hydrolysis products. Since the preparation processes of these composites are simple and cost-effective and the hydrolysis of these composites achieves efficient hydrogen release, it is promising that this kind of composites can be applied in hydrogen generation.  相似文献   

14.
Experiments were performed to add hydrogen to liquefied petroleum gas (LPG) and methane (CH4) to compare the emission and impingement heat transfer behaviors of the resultant LPG–H2–air and CH4–H2–air flames. Results show that as the mole fraction of hydrogen in the fuel mixture was increased from 0% to 50% at equivalence ratio of 1 and Reynolds number of 1500 for both flames, there is an increase in the laminar burning speed, flame temperature and NOx emission as well as a decrease in the CO emission. Also, as a result of the hydrogen addition and increased flame temperature, impingement heat transfer is enhanced. Comparison shows a more significant change in the laminar burning speed, temperature and CO/NOx emissions in the CH4 flames, indicating a stronger effect of hydrogen addition on a lighter hydrocarbon fuel. Comparison also shows that the CH4 flame at α = 0% has even better heat transfer than the LPG flame at α = 50%, because the longer CH4 flame configures a wider wall jet layer, which significantly increases the integrated heat transfer rate.  相似文献   

15.
The effects of B2O3–Bi2O3–PbO (BBP) frit on the electrochemical performance, electrical conductivity, and thermal expansion of LaBaCo2O5+δ (LBCO) cathode were investigated. BBP frit was found to be effective in lowering the sintering temperature of LBCO cathode by about 200 °C and in improving its electrochemical performance within the intermediate-temperature range of 600–800 °C. LBCO with 5 wt.% BBP frit cathode based on Sm0.2Ce0.8O1.9 electrolyte showed the best electrochemical performance, i.e., the lowest area-specific resistance (ASR) and cathodic overpotential. The ASR values were about 64.1%, 66.1%, and 74.5% lower than those of LBCO at 700, 750, and 800 °C, respectively. The cathodic overpotential decreased from 51.0 mV for LBCO to 8.2 mV at a current density of 0.2 A cm−2 at 700 °C. The electrical conductivity of LBCO with 5 wt.% BBP frit was about 320–330 S cm−1 at 600–800 °C in air.  相似文献   

16.
La–Mg–Ni-based La0.75Mg0.25Ni3.3Co0.5 hydrogen storage alloy was synthesized by high-energy mechanical milling blending of the La0.75Ni3.3Co0.5 as-cast alloy prepared by vacuum arc melting and elemental Mg, and subsequent isothermal annealing. The chemical compositions, microstructures and electrochemical properties of the as-cast La0.75Ni3.3Co0.5 alloy, the milled and annealed La0.75Mg0.25Ni3.3Co0.5 alloys were investigated, respectively, by inductively coupled plasma, X-ray diffraction, differential scanning calorimetry, X-ray photoelectron spectroscopy and electrochemical measurements. The results show that single LaNi5 phase exists in the as-cast La0.75Ni3.3Co0.5 alloy. The milled La0.75Mg0.25Ni3.3Co0.5 alloy contains multiphase structure, besides the main LaNi5 phase, a small amount of (La,Mg)Ni3 and (La,Mg)2Ni7 new phases are observed as well. The annealed La0.75Mg0.25Ni3.3Co0.5 alloy is composed of LaNi5 and (La,Mg)2Ni7 phases. Annealing treatment can result in (La,Mg)Ni3 phase converting into (La,Mg)2Ni7 phase. The electrochemical measurements indicate that the maximum discharge capacity and discharge potential characteristic of the as-cast La0.75Ni3.3Co0.5 alloy are better than those of the milled La0.75Mg0.25Ni3.3Co0.5 alloy, whereas worse than those of the annealed La0.75Mg0.25Ni3.3Co0.5 alloy. The cyclic stability of the milled La0.75Mg0.25Ni3.3Co0.5 alloy is slightly better than that of the as-cast La0.75Ni3.3Co0.5 alloy, whereas obviously worse than that of the annealed La0.75Mg0.25Ni3.3Co0.5 alloy. Overall, the annealed La0.75Mg0.25Ni3.3Co0.5 alloy performs the best in the maximum discharge capacity, discharge potential characteristic and cycling stability.  相似文献   

17.
Cobalt nanoparticles on an amorphous Si3N4 matrix were synthesized by direct ball-milling of Co and Si3N4 powders for an improvement of their electrochemical performance. The microstructure, morphology and chemical state of the ball-milled Co–Si3N4 composites are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The electrochemical performance of Co–Si3N4 composites was investigated by galvanostatic charge–discharge process and cyclic voltammetry (CV) technique. It is found that metallic Co nanoparticles of 10–20 nm in size are highly dispersed on the amorphous inactive Si3N4 matrix after the ball-milling. The composite with a Co/Si molar ratio of 2/1 shows the optimized electrochemical performance, including discharge capacity and cycle stability. The formation of Co nanoparticles with a good reaction activity is responsible for the discharge capacity of the composites. The reversible faradic reaction between Co and β-Co(OH)2 is dominant for ball-milled Co–Si3N4 composite. The surface modification of the hydrogen storage PrMg12–Ni composites using Co–Si3N4 composites can enhance the initial discharge capacity based on the hydrogen electrochemical oxidation and Co redox reaction.  相似文献   

18.
Catalysts with high nickel concentrations 75%Ni–12%Cu/Al2O3, 70%Ni–10%Cu–10%Fe/Al2O3 were prepared by mechanochemical activation and their catalytic properties were studied in methane decomposition. It was shown that modification of the 75%Ni–12%Cu/Al2O3 catalyst with iron made it possible to increase optimal operating temperatures to 700–750 °C while maintaining excellent catalyst stability. The formation of finely dispersed Ni–Cu–Fe alloy particles makes the catalysts stable and capable of operating at 700–750 °C in methane decomposition to hydrogen and carbon nanofibers. The yield of carbon nanofibers on the modified 70%Ni–10%Cu–10%Fe/Al2O3 catalyst at 700–750 °C was 150–160 g/g. The developed hydrogen production method is also efficient when natural gas is used as the feedstock. An installation with a rotating reactor was developed for production of hydrogen and carbon nanofibers from natural gas. It was shown that the 70%Ni–10%Cu–10%Fe/Al2O3 catalyst could operate in this installation for a prolonged period of time. The hydrogen concentration at the reactor outlet exceeded 70 mol%.  相似文献   

19.
An innovative, nanostructured composite, anode electrocatalyst, material has been developed for the electrolytic splitting of (100%) H2S feed content gas operating at 135 kPa and 150 °C. A new class of anode electrocatalyst with general composition, RuO2–CoS2 has shown great stability and desired properties at typical operating conditions. This configuration showed stable electrochemical operation over the period of 24 h and also exhibited a maximum current density of (0.019 A/cm2). The kinetic behaviors of various anode-based electrocatalysts demonstrated that, exchange current density, which is a direct measure of the electrochemical reaction, increased with RuO2–CoS2-based anodes. Moreover, high levels of feed utilization were possible using these materials. Electrochemical performance, current density, and sulfur tolerance were enhanced compared to the other tested anode configurations. The structural, microstructural and surface behavior of RuO2–CoS2 anode electrocatalyst was investigated in detail.  相似文献   

20.
The effect of MgFe2O4 on the hydrogen storage properties of the composite Na3AlH64LiBH4 was studied for the first time, where it was found that MgFe2O4 addition decreased the onset desorption temperature of Na3AlH64LiBH4. Hydrogen (~9.5 wt%) was released in three stages and the dehydrogenation temperatures were reduced to 80 °C, 350 °C, and 430 °C for the first, second, and third stage, respectively. The absorption kinetics of Na3AlH64LiBH4 was also significantly improved due to the catalytic effect of MgFe2O4. Using Kissinger analysis, the apparent activation energies of decomposition of the Li3AlH6 and NaBH4 stages in Na3AlH64LiBH4-10 wt% MgFe2O4 were calculated to be 72 and 141 kJ/mol, respectively. These values were considerably lower than the corresponding values for the undoped composite. X-ray diffraction analysis revealed the formation of new products such as MgO and Fe during the heating process. Our results suggest that MgFe2O4 enhanced the hydrogen storage properties of Na3AlH64LiBH4 through the formation of active species, such as MgO and Fe.  相似文献   

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