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1.
In this work, the Mg90Y1.5Ce1.5Ni7 sample is successfully prepared by combining the vacuum induction melting and the mechanical milling. The phase composition and microstructure characteristics are studied by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy measurements. The hydrogenated sample is composed of MgH2, Mg2NiH4, CeH2.73 phases, whereas only the MgH2 and Mg2NiH4 phases are decomposed during dehydrogenation. The hydrogen storage properties of Mg90Y1.5Ce1.5Ni7 samples are measured by semi-automatic Sievert type apparatus. It is found that the samples could be fully activated within three cycles of absorption and dehydrogenation, with a reversible hydrogen storage capacity of about 5.6 wt%. Also, the “optimal hydrogenation temperature” is reduced to 200 °C, and the dehydrogenation activation energy is calculated to be 68.2 kJ/mol and 65.8 kJ/mol by using the Arrhenius and Kissinger equations, respectively. This work provides a scientific approach to promote the practical application of Mg-based alloy.  相似文献   

2.
The effects of the type and amount of transition metal catalyst on the microstructure and hydrogen storage performance of La5Mg85Ni10 + x wt.% M (x = 1, 3, 5, 7; M = TiF3, NbF5, Cr2O3) alloys milled for 10 h have been investigated. The evolution of microstructure and phase of catalyzed alloys in the absorption/desorption process have been characterized by XRD and HRTEM. The results show that the hydrogen storage capacity of the alloy decreases as the catalyst increases. On the one hand, the catalytic effects of different amount of catalyst TiF3 were studied. TiF3 exists in form of MgF2 and TiH2 phases and Ea decreases firstly and then increases as the amount of TiF3 increases. When 5 wt.% TiF3 is added, the hydrogen desorption activation energy shows the lowest Ea = 45.2 kJ/mol. On the other hand, the catalytic effects of TiF3, Cr2O3 and NbF5 are compared in detail. It was found that TiF3 has better catalytic effect than Cr2O3 and NbF5 due to TiF3 nanoparticles can refine the grains better, provide hydrogen diffusion channels and reduce the nucleation driving force of the alloys.  相似文献   

3.
Ternary eutectic Mg76.87Ni12.78Y10.35 (at. %) ribbons with mixed amorphous and nanocrystalline phases were prepared by melt spinning. The microstructures of the melt-spun, hydrogenated and dehydrogenated samples were examined and compared by X-ray diffraction and transmission electron microscopy. The amorphous structure transforms into a thermally stable nanocrystalline structure with a grain size of about 5 nm during hydrogen ab/desorption cycles. The Mg, Mg2Ni and phases with Y in the melt-spun state transform into MgH2, Mg2NiH4, Mg2NiH0.3, YH2 and YH3 after hydrogenation, and transform back to Mg, Mg2Ni and YH2 upon subsequent dehydrogenation. The reaction enthalpy (ΔH) and entropy (ΔS) of the higher plateau pressure corresponding to Mg2Ni hydride formation are −53.25 kJ mol−1 and −107.74 J K−1 mol−1, respectively. The amorphous/nanocrystalline structure effectively reduces the enthalpy and entropy of Mg2Ni hydride formation, but has little effect on Mg. The activation energy for dehydrogenation of the hydrogenated ribbons is 69 kJ mol−1. This suggests that Mg–Ni–Y with ternary eutectic composition can form an amorphous/nanocrystalline structure by melt spinning, and this nanostructure efficiently improves the thermodynamics and kinetics for hydrogen storage.  相似文献   

4.
In order to reduce the obstacle influence of coarse Mg2Ni phase on hydrogen absorption kinetics in Mg–Ni alloys, aluminum was doped and Mg77Ni23-xAlx (x = 0, 3, 6, 9) alloys were prepared. The results show that AlNi phase was formed when Al was added, the size of primary Mg2Ni phase decreases with increasing Al content till 6 at.%, while primary Mg2Ni phase was diminished and primary Mg phase was formed when Al content increased to 9 at.%. The initial hydrogenation rates of Mg77Ni23-xAlx alloys were increased, which is resulted from the refined primary Mg2Ni and the catalytic AlNi phase. More importantly, the hydrogenation rates and capacities were significantly improved at 150 °C, especially for the Mg77Ni17Al6 alloy. The apparent activation energy of the Mg77Ni17Al6 alloy for hydrogenation was reduced to 73.68 kJ/mol from 102.27 kJ/mol of the Mg77Ni23 alloy. Its enthalpy changes for hydrogenation at low and high platforms are 72.3 kJ/mol and 53.9 kJ/mol, respectively. The multiple channels and short distance for hydrogen atoms diffusion provided by refined primary Mg2Ni phase, the solid dissolution of Al in Mg2Ni lattice, and catalytic effect of AlNi on hydrogenation, leading to the improvement of the hydrogen storage properties.  相似文献   

5.
The effects of Ni and Co addition on the hydrogen storage properties of Mg3Mm alloy was studied by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX) and pressure-composition isotherm (PCI) measurement. The hydrogen absorption kinetics and the thermodynamic parameters (apparent ΔH, ΔS) for Mg3Mm dehydrogenation reactions in Mg3Mm, Mg3MmNi0.1 and Mg3MmNi0.1Co0.1 alloys have been also investigated. The maximum hydrogen storage content of Mg3Mm, Mg3MmNi0.1 and Mg3MmNi0.1Co0.1 alloys was improved due to that the addition of Ni and/or Co further spurred the MmH3 phase transforming to MmH2 phase. On the other side, the kinetics curves show the addition of Co could enhance hydrogen absorption rate while the addition of Ni change the hydrogenation reaction mechanism.  相似文献   

6.
In this paper, we report the microstructure and hydrogen storage properties of TiFe-based alloys containing chromium (Cr), manganese (Mn) and yttrium (Y). Four alloy samples with chemical composition of TiFe0.9Cr0.1, TiFe0.9Cr0.1Y0.05, TiFe0.9Mn0.1 and TiFe0.9Mn0.1Y0.05 were prepared by arc melting, and the effects of alloying elements Cr, Mn and Y on microstructure and hydrogenation kinetics and thermodynamics were investigated in detail. It was found that all the four alloys have the main phase of TiFe intermetallic compound. A small amount of secondary phase can be also detected in the alloy samples. Cr substituted alloys have larger lattice parameters than that of Mn substituted alloys. Y in the alloys is mainly existed in the form of α-Y phase, and it transform into YH3 during hydrogenation process. Very sloped equilibrium plateau regions are observed in Cr substituted alloys, while the Mn substituted alloys have flat equilibrium plateaus. Y addition has almost no influence on pressure–composition–isotherm (pcT) curves of Cr substituted alloy, but slightly decrease the equilibrium plateaus of Mn substituted alloys. Hydrogen absorption and desorption kinetics strongly depend on the equilibrium plateau pressures. As a result, the Cr substituted alloys with lower equilibrium plateau pressure have faster hydrogen absorption and slower desorption kinetics compared with Mn substituted alloys. The Cr substituted alloys have poor powdering resistance compared with Mn substituted alloys during hydrogenation cycles, which can be ascribed to the higher hardness of alloy matrix caused by Cr substitution.  相似文献   

7.
In this study, we investigated the microstructures, hydrogen absorption kinetics, and oxide layers of TiFe and Ti1.2Fe hydrogen storage alloys. Whereas the TiFe alloy has a single phase, the Ti1.2Fe alloy is composed of three phases: TiFe, Ti2Fe, and Ti4Fe. Under no thermal activation process, the TiFe alloy does not absorb hydrogen, though the Ti1.2Fe alloy starts to absorb hydrogen after 4 min of incubation time. From the XPS results, it is revealed that the Ti concentration in the oxide layer on the Ti4Fe phase is higher than that on the TiFe phase, indicating that the Ti concentration in the oxide layer would be important in improving hydrogen absorption kinetics. Based on these results, the hydrogen absorption kinetics could be improved by adjusting composition, enabling the formation of a Ti-rich oxide layer.  相似文献   

8.
For pushing Mg-based alloys developing to the practical applications, nano-CeO2 powders were added into the mechanical alloyed (MA) Mg90Al10 alloy. The aim of it is to improve the thermodynamics and kinetics through generating new intermetallic compound, reducing the grain size and increasing the solid solubility of Al in Mg. XRD analysis showed that adding nano-CeO2 powder causes the generation of Mg17Al12 phase and grain refinement of the MA Mg90Al10 + x wt% CeO2 (x = 1, 3, 5 and 8) composites. It also increases the solid solubility of Al in Mg, while results in the reduction of Mg lattice volume. The dehydrogenation enthalpy (ΔHde), calculated from Van't Hoff equation, is reduced from 75.43 kJ mol−1 H2 for the MA Mg90Al10 alloy to 74.22, 72.70, 70.28 and 73.71 kJ mol−1 H2 for the MA Mg90Al10 + x wt% CeO2 (x = 1, 3, 5 and 8) composites, respectively. The increased grain boundaries, caused by the grain refinement and formation of the mutilphase structure, are beneficial to reduce the dehydrogenation activation energy (Ede(a)). It is obtained through Johnson-Mehl-Avrami-Kolmogorov model, which is 162.06, 121.86, 103.73, 101.83 and 109.08 kJ mol−1 H2 for the MA Mg90Al10 + x wt% CeO2 (x = 0, 1, 3, 5 and 8) composites, respectively.  相似文献   

9.
In this experiment, the Mg-based hydrogen storage alloys SmMg11Ni and SmMg11Ni + 5 wt.% MoS2 (named SmMg11Ni-5MoS2) were prepared by mechanical milling. By comparing the structures and hydrogen storage properties of the two alloys, it could be found that the addition of MoS2 has brought on a slight change in hydrogen storage thermodynamics, an obvious decrease in hydrogen absorption capacity, an obvious catalytic action on hydrogen desorption reaction, and a lowered onset desorption temperature from 557 to 545 K. Additionally, the addition of MoS2 could dramatically improve the alloy in its hydrogen absorption and desorption kinetics. To be specific, the hydrogen desorption times of 3 wt.% H2 at 593, 613, 633 and 653 K were measured to be 1488, 683, 390 and 192 s respectively for the SmMg11Ni alloy, which were reduced to 938, 586, 296 and 140 s for the MoS2 catalyzed SmMg11Ni alloy at identical conditions. The activation energies of the alloys with and without MoS2 for hydrogen desorption are 87.89 and 100.31 kJ/mol, respectively. The 12.42 kJ/mol decrease is responsible for the ameliorated hydrogen desorption kinetics by adding catalyst MoS2.  相似文献   

10.
Mechanical milling is widely recognized as the best method to prepare nano-structured magnesium based hydrogen storage materials. The composites La7Sm3Mg80Ni10 + 5 wt% TiO2 (named La7Sm3Mg80Ni10–5TiO2) whose structures are nano-crystal and amorphous accompanied by great hydrogen absorption and desorption properties were fabricated by mechanical milling. The research focuses on the effect of milling duration on the thermodynamics and dynamics. The instruments of researching the gaseous hydrogen storing performances include Sievert apparatus, DSC and TGA. The calculation of dehydrogenation activation energy was realized by applying Arrhenius and Kissinger formulas. The calculation results show the specimen milled for 10 h exhibits the optimal activation performance and hydrogenation and dehydrogenation kinetics. Extending or shrinking the milling duration will lead to the degradation of hydrogen storage performances. The as-milled (10 h) alloy at the full activated state can absorb 4 wt% hydrogen in 87 s at 473 K and 3 MPa and release 3 wt% H2 in 288 s at 573 K and 1 × 10−4 MPa. The changed milling durations have little impact on the thermodynamic properties of experimental samples and the enthalpy change (ΔH) of the alloy milled for 10 h is 74.23 kJ/mol. Moreover, it is found that the as-milled (10 h) alloy displays the minimum apparent activation energy of dehydrogenation (59.1 kJ/mol), suggesting the optimal hydrogen storing property of the as-milled (10 h) alloy.  相似文献   

11.
Mg(AlH4)2 submicron rods with 96.1% purity have been successfully synthesized in a modified mechanochemical reaction process followed by Soxhlet extraction. ∼9.0 wt% of hydrogen is released from the as-prepared Mg(AlH4)2 at 125–440 °C through a stepwise reaction. Upon dehydriding, Mg(AlH4)2 decomposes first to generate MgH2 and Al. Subsequently, the newly produced MgH2 reacts with Al to form a Al0.9Mg0.1 solid solution. Finally, further reaction between the Al0.9Mg0.1 solid solution and the remaining MgH2 gives rise to the formation of Al3Mg2. The first step dehydrogenation is a diffusion-controlled reaction with an apparent activation energy of ∼123.0 kJ/mol. Therefore, increasing the mobility of the species involved in Mg(AlH4)2 will be very helpful for improving its dehydrogenation kinetics.  相似文献   

12.
The LaNi5 intermetallic compound is an AB5 type hydrogen storage alloy which exhibits low operating temperature, easy activation, low pressure and tolerance to impurities. In this study, LaNi4.7-x Al0.3Bix (x = 0.0, 0.1, 0.2, 0.3) alloys were produced by melt-spinning technique and the effects of Al and Bi additions on the microstructure, thermal and hydrogen storage properties of LaNi5 were investigated. The results showed that substitution of Ni with Al led to a desired decrease in absorption/desorption plateau pressure and hysteresis without a decrease in hydrogen storage capacity. In contrast, Bi substitution with Ni increased the absorption/desorption plateau pressure, reduced the hydrogen capacity and increased pulverization resistance of the alloy due to the formation of BiLa and AlNi3 intermetallic phases at the grain boundaries.  相似文献   

13.
The rare earth elements are believed to catalyze the reversible reaction between magnesium and hydrogen and reduce the thermal stability of MgH2 by weakening the Mg–H bond. This study focuses on investigating the effect of Ce partial substitution of La on the comprehensive hydrogen storage performances of La10-xCexMg80Ni10 (x = 0–4) alloys (prepared by vacuum induction melting). The phase composition and microstructure were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and high-resolution transmission electron microscopy (HRTEM). The thermodynamics and kinetics of isothermal reactions were measured by the automatic Sievert apparatus. Non-isothermal dehydrogenation performance of the alloys was researched by thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC). All the experimental alloys have a large capacity of hydrogen absorption and desorption and the kinetics of the Ce containing alloys is better. The additive Ce exists in the solid solution of alloy and results in the refinement of grain, making the stability of the hydride visibly lower, which is the reason for the decline in the initial dehydrogenation temperature and enthalpy (ΔH) of the hydride. Besides, the dehydrogenation activation energy of the alloys is distinctly reduced by composition adjustment, which indicates the improved hydrogen storage performances.  相似文献   

14.
Transition metals and rare-earth elements have excellent catalytic effects on improving the de-/hydrogenation properties of Mg-based alloys. In this study, a small amount of La is used to substitute the Ni in Mg98Ni2 alloy, and some Mg98Ni2-xLax (x = 0, 0.33, 0.67, and 1) alloys show the better overall hydrogen storage properties. The effects of La on the solidification and de-/hydrogenation behaviors of the alloys are revealed. The results indicate that different factors dominate the processes of hydrogen absorption and desorption. The Mg98Ni1·67La0.33 alloy absorb 7.04 wt % hydrogen at 300 °C, with the highest isothermal absorption rate, the Mg98Ni1·33La0.67 hydride show the highest isothermal desorption rates and the lowest peak desorption temperature of 327 °C. The La addition can increase the driving force of hydrogenation, thus the hydrogenation rates and capacities of the Mg98Ni1·67La0.33 and Mg98Ni1·33La0.67 alloys are improved. The formation of refined eutectic structures is a key factor that facilitates the desorption processes of the Mg98Ni2-xLax hydrides with x = 0.67 and 1. High-density LaH3 nanophses are in-situ formed from the LaMgx (8.5 < x < 12) phase, which results in the improved de-/hydrogenation properties. The further La addition deteriorates the hydrogen storage properties of Mg98Ni2-xLax alloy.  相似文献   

15.
In order to improve the hydrogenation/dehydrogenation properties of the Mg/MgH2 system, the nickel hydride complex NiHCl(P(C6H11)3)2 has been added in different amounts to MgH2 by planetary ball milling. The hydrogen storage properties of the formed composites were studied by different thermal analyses methods (temperature programmed desorption, calorimetric and pressure-composition-temperature analyses). The optimal amount of the nickel complex precursor was found to be of 20 wt%. It allows to homogeneously disperse 1.8 wt% of nickel active species at the surface of the Mg/MgH2 particles. After the decomposition of the complex during MgH2 dehydrogenation, the formed composite is stable upon cycling at low temperature. It can release hydrogen at 200 °C and absorb 6.3 wt% of H2 at 100 °C in less than 1 h. The significantly enhanced H2 storage properties are due to the impact of the highly dispersed nickel on both the kinetics and thermodynamics of the Mg/MgH2 system. The hydrogenation and dehydrogenation enthalpies were found to be of −65 and 63 kJ/mol H2 respectively (±75 kJ/mol H2 for pure Mg/MgH2) and the calculated apparent activation energies of the hydrogen uptake and release processes are of 22 and 127 kJ/mol H2 respectively (88 and 176 kJ/mol H2 for pure Mg/MgH2). The change in the thermodynamics observed in the formed composite is likely to be due to the formation of a Mg0.992Ni0.008 phase during dehydrogenation/hydrogenation cycling. The impact of another hydride nickel precursor in which chloride has been replaced by a borohydride ligand, namely NiH(BH4)(P(C6H11)3)2, is also reported.  相似文献   

16.
The Mg-based hydrogen storage alloy with multiple platforms is successfully prepared by ball milling Co powder and Mg-RE-Ni precursor alloy, and its hydrogen storage behavior was investigated in detail by XRD, EDS, TEM, PCI, and DSC methods. The ball-milled alloy consists of the main phase Mg, the catalytic phases Mg2Ni, Mg2Co as well as a small amount of Mg12Ce, and convert into the MgH2–CeH2.73-Mg2NiH4–Mg2CoH5 composite after hydrogenation. The composite has three PCI platforms corresponding to the reversible de/hydrogenation reaction of Mg/MgH2, Mg2Ni/Mg2NiH4 and Mg6Co2H11/Mg2CoH5. Among them, the transformation between Mg2Ni and Mg2NiH4 triggers the “spill-over” effect which promote the decomposition of MgH2 phases and enhances the hydrogen desorption kinetics. Meanwhile, the conversion of the Mg6Co2H11 to Mg2CoH5 phase induces the “chain reaction” effect, which leads to preferential nucleation of Mg phase and improves the hydrogen absorption kinetics. Therefore, the Mg-RE-Ni-Co alloy has a double improvement on hydrogen absorption and desorption kinetics. Concretely, the alloy has an optimal hydrogen absorption temperature of 200 °C, at which it can absorb 5.5 wt. % H2 within 40 s. Under the conditions, the capacity of absorption almost reaches the maximum reversible value (about 5.6 wt. %). Besides, the alloy has a dehydrogenation activation energy of 67.9 kJ/mol and can desorb 5.0 wt. % H2 within 60 min at the temperature of 260 °C.  相似文献   

17.
Hydrogen-based fuels demand high-density storage that can operate at ambient temperatures. Pd and its alloys are the most studied metal hydrides for hydrogen fuel cell applications. This study presented an alternative Pd alloy for hydrogen storage that can store and release hydrogen at room temperature. The surface of the most commonly studied Pd (110) was modified with Au and Rh such that the hydrogen adsorption energy was 0.49 eV and the release temperature was 365 K. Both values are quite close to the optimal values for the adsorption energy and release temperature of a hydrogen fuel cell in real use. We further show that the modified Pd (110) surface has significantly stronger oxygen evolution reaction (OER) catalytic properties than the pure Pd (110) surface.  相似文献   

18.
The hydrogenation characteristics and hydrogen storage kinetics of the melt-spun Mg10NiR (R = La, Nd and Sm) alloys have been studied comparatively. It is found that the Mg10NiNd and Mg10NiSm alloys are in amorphous state but the Mg10NiLa alloy is composed of an amorphous phase and minor crystalline La2Mg17 after melt-spinning. The alloys can be hydrogenated into MgH2, Mg2NiH4 and a rare earth metal hydride RHx. The rare earth metal hydride and Mg2NiH4 synergistically provide a catalytic effect on the hydrogen absorption–desorption reactions in the Mg−H2 system. The hydrogen storage kinetics is not influenced by different rare earth metal hydrides but by the particle size of the rare earth metal hydrides.  相似文献   

19.
Practical challenges of metal hydrides for hydrogen storage such as magnesium hydride, lie predominantly in improving hydrogen absorption kinetics and capacity. Approaches to improving kinetics of Mg commonly include changing particle geometry, reducing crystallite size and coating with catalytic transition metals such as Ni. This study is aimed at improving the hydrogen storage kinetics and capacity of Mg by a novel approach utilizing high aspect ratio powders (thin metal flakes with large diameters) coated with a Ni nano-catalyst. A high speed orbiting ball media (HSOBM) processor was utilized to fabricate the flake-shaped materials. Mg flakes effectively coated with Ni nano-catalyst using dry mechanical coating were found to possess more favorable hydrogen absorption/desorption characteristics and improved hydrogen storage capacity than traditional spherical particles. Geometric shape was shown to be a vital factor in hydrogen absorption kinetics and its effects proved to be dominant over those of crystallite size.  相似文献   

20.
Hydrogen absorption in a metal hydride tank is generally studied based on a heat and mass transfer analysis. The originality of this investigation is that the phase transformation from a solid (α phase) to hydride (β phase) solution is included in the hydrogen absorption mechanism. Toward this end, a modelling of the equilibrium pressure, composition (absorbed or desorbed hydrogen atoms per metal atoms), and isothermal curves of a LaNi5 alloy is performed. Moreover, a kinetic model is developed taking into account the steps of hydrogen absorption and desorption (i.e., physisorption, chemisorption, surface penetration, nucleation and growth of the hydride phase and diffusion).  相似文献   

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