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1.
Mg hydride is a competitive candidates for hydrogen storage based on its high gravimetric hydrogen capacity and accessibility. In this study, a small amount of KOH and graphene were added into MgH2 by high energy ball milling. MgH2 doped with both KOH and graphene has a greatly improved hydrogen storage performance. The existence of graphene and the in-situ formed KMgH3 and MgO decreased activation energy of MgH2 to 109.89 ± 6.03 kJ/mol. The both KOH and graphene doped sample has a reversibly capacity of 5.43 wt % H2 and can released H2 as much as 6.36 times and 1.84 times faster than those of undoped sample and only KOH doped sample at 300 °C, respectively. The addition of graphene not only can provide more “H diffusion channels”, but also can disperse the catalyst.  相似文献   

2.
The present investigation deals with the synthesis of ternary transition metal alloy nanoparticles of FeCoNi and graphene templated FeCoNi (FeCoNi@GS) by one-pot reflux method and there use as a catalyst for hydrogen sorption in MgH2. It has been found that the MgH2 catalyzed by FeCoNi@GS (MgH2: FeCoNi@GS) has the onset desorption temperature of ~255 °C which is 25 °C and 100 °C lower than MgH2 catalyzed by FeCoNi (MgH2: FeCoNi) (onset desorption temperature 280 °C) and the ball-milled (B.M) MgH2 (onset desorption temperature 355 °C) respectively. Also MgH2: FeCoNi@GS shows enhanced kinetics by absorbing 6.01 wt% within just 1.65 min at 290 °C under 15 atm of hydrogen pressure. This is much-improved sorption as compared to MgH2: FeCoNi and B.M MgH2 for which hydrogen absorption is 4.41 wt% and 1.45 wt% respectively, under the similar condition of temperature, pressure and time. More importantly, the formation enthalpy of MgH2: FeCoNi@GS is 58.86 kJ/mol which is 19.26 kJ/mol lower than B.M: MgH2 (78.12 kJ/mol). Excellent cyclic stability has also been found for MgH2: FeCoNi@GS even up to 24 cycles where it shows only negligible change from 6.26 wt% to 6.24 wt%. A feasible catalytic mechanism of FeCoNi@GS on MgH2 has been put forward based on X-ray diffraction (XRD), Raman spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Photoelectron Spectroscopy (XPS), and microstructural (electron microscopic) studies.  相似文献   

3.
Effect of a MgF2 catalyst, prepared by ball-milling, on the hydrogen desorption ability of commercial MgH2 was investigated. When MgH2 was catalyzed with a MgF2 composite, it exhibited good cyclability and sharp faceting, with a small grain size (around 10 nm), which differs from those of pure MgH2. The addition of the MgF2 catalyst suggests that the F anion could significantly contribute to the cyclability of Mg particles and aid in the inhibition of MgH2 grain growth.  相似文献   

4.
The effects of MnFe2O4 nanopowder synthesised via a simple ‘hydrothermal’ method on the hydrogen storage properties of MgH2 are investigated for the first time. The particle size of the as-synthesised MnFe2O4 nanoparticles is determined to be about 10 nm. We observe that MnFe2O4 catalyst decreases the decomposition temperature of MgH2 and enhances the sorption kinetics. Interestingly, the onset hydrogen desorption temperature of 10 wt% MnFe2O4-doped MgH2 sample gets lowered from 350 °C to 240 °C with faster kinetics, and the sample shows an average dehydrogenation rate 8–9 times faster than that of the as-milled MgH2 sample. By adding 10 wt% of as-prepared MnFe2O4 to MgH2, approximately 5.5 wt% hydrogen can be absorbed in 10 min at 200 °C. In contrast, the un-doped MgH2 sample absorbed only 4.0 wt% hydrogen in the same period of time. From the Kissinger analysis, the apparent activation energy for hydrogen released in the MnFe2O4-added MgH2 composite is found to be 108.42 kJ/mol, which is much lower than the activation energy for hydrogen released in the as-milled MgH2 (146.57 kJ/mol). It is believed that the in situ formed Fe particle and Mn-containing phases together play a synergistic role in remarkably improving MgH2 storage properties.  相似文献   

5.
Currently, magnesium hydride (MgH2) as a solid-state hydrogen storage material has become the subject of major research owing to its good reversibility, large hydrogen storage capacity (7.6 wt%) and affordability. However, MgH2 has a high decomposition temperature (>400 °C) and slow desorption and absorption kinetics. In this work, BaMnO3 was synthesized using the solid-state method and was used as an additive to overcome the drawbacks of MgH2. Interestingly, after adding 10 wt% of BaMnO3, the initial desorption temperature of MgH2 decreased to 282 °C, which was 138 °C lower than that of pure MgH2 and 61 °C lower than that of milled MgH2. For absorption kinetics, at 250 °C in 2 min, 10 wt% of BaMnO3-doped MgH2 absorbed 5.22 wt% of H2 compared to milled MgH2 (3.48 wt%). Conversely, the desorption kinetics also demonstrated that 10 wt% of BaMnO3-doped MgH2 samples desorbed 5.36 wt% of H2 at 300 °C within 1 h whereas milled MgH2 only released less than 0.32 wt% of H2. The activation energy was lowered by 45 kJ/mol compared to that of MgH2 after the addition of 10 wt% of BaMnO3. Further analyzed by using XRD revealed that the formation of Mg0·9Mn0·1O, Mn3O4 and Ba or Ba-containing enhanced the performance of MgH2.  相似文献   

6.
The influences of Nb-containing oxides and ternary compound in hydrogen sorption performance were investigated. As faster desorption kinetic and lower activation energy were reported by addition of a ternary compound catalyst such as K2NiF6, the influence of KNbO3 on hydrogen storage properties of MgH2 has been investigated for the first time. The MgH2 - KNbO3 composite desorbed 3.9 wt% of hydrogen within 10 min, while MgH2 and MgH2-Nb₂O₅ composites desorbed 0.66 wt% and 3.2 wt% respectively under similar condition. For MgH2 with other Nb-contained catalysts such as Nb, NbO and Nb₂O3, the desorption rate was almost the same as the one registered for as-milled MgH2. The analysis of differential scanning calorimetry (DSC) showed that MgH2-KNbO3 composite started to release hydrogen at ∼335 °C which is 50 °C lower compared to as-milled MgH2 without any additives. The activation energy for the hydrogen desorption was estimated to be about 104 ± 6.8 kJ mol−1 for this material, while for the as-milled MgH2 was about 165 ± 2.0 kJ mol−1. It is believed that Nb-ternary oxide catalyst (KNbO3) showed a good catalytic effect and enhance the sorption kinetics of MgH2.  相似文献   

7.
In this work, we have investigated the hydrogen release and uptake pathways storage properties of the MgH2Na3AlH6 with a molar ratio of 4:1 and doped with 10 wt% of TiF3 using a mechanical alloying method. The doped composite was found to have a significant reduction on the hydrogen release temperature compared to the un-doped composite based on the temperature-programme-desorption result. The first stage of the onset desorption temperature of MgH2Na3AlH6 was reduced from 170 °C to 140 °C with the addition of the TiF3 additive. Three dehydrogenation steps with a total of 5.3 wt% of released hydrogen were observed for the 4MgH2Na3AlH6-10 wt% TiF3 composite. The re/dehydrogenation kinetics of 4MgH2Na3AlH6 system were significantly improved with the addition of TiF3. Kissinger analyses showed that the apparent activation energy, EA, of the 4MgH2Na3AlH6 doped composite was 124 kJ/mol, 16 kJ/mol and 34 kJ/mol lower for un-doped composite and the as-milled MgH2, respectively. It was believed that the enhancements of the MgH2Na3AlH6 hydrogen storage properties with the addition of TiF3 were due to formation of the NaF, the AlF3 and the Al3Ti species. These species may played a synergetic catalytic role in improving the hydrogenation properties of the MgH2Na3AlH6 system.  相似文献   

8.
The search for efficient materials for onboard hydrogen storage applications is an emerging research field. Using density functional calculations, we demonstrate Zn substituted MgH2 as a potential material for hydrogen storage. We predicted the ground state crystal structure of ZnH2 which is found to be Pna21 (orthorhombic) structure with meta-stable behavior. The structural phase stability and phase transition of Mg1−xZnxH2 systems have been analyzed. The H site energy of Mg1−xZnxH2 systems is calculated to understand the hydrogen desorption process. Our calculations suggest that Zn substitution reduces the stability of MgH2, thereby it may reduce the decomposition temperature of MgH2. The band structure and density of states calculations reveal that the Mg1−xZnxH2 systems are insulators. The chemical bonding behavior of Mg1−xZnxH2 systems is established as iono-covalent in nature. Moreover, Zn substitution in MgH2 induces disproportionate MgH bonds which could also contribute the reduction in the decomposition temperature as well as H sorption kinetics.  相似文献   

9.
Magnesium-based hydrogen storage materials (MgH2) are promising hydrogen carrier due to the high gravimetric hydrogen density; however, the undesirable thermodynamic stability and slow kinetics restrict its utilization. In this work, we assist the de/hydrogenation of MgH2 via in situ formed additives from the conversion of an MgNi2 alloy upon de/hydrogenation. The MgH2–16.7 wt%MgNi2 composite was synthesized by ball milling of Mg powder and MgNi2 alloy followed by a hydrogen combustion synthesis method, where most of the Mg converted to MgH2, and the others reacted with the MgNi2 generating Mg2NiH4, which produced in situ Mg2Ni during dehydrogenation. Results showed that the Mg2Ni and Mg2NiH4 could induce hydrogen absorption and desorption of the MgH2, that it absorbed 2.5 wt% H2 at 473 K, much higher than that of pure Mg, and the dehydrogenation capacity increased by 2.6 wt% at 573 K. Besides, the initial dehydrogenation temperature of the composite under the promotion of Mg2NiH4 decreased greatly by 100 K, whereas it is 623 K for MgH2. Furthermore, benefiting from the catalyst effect of Mg2NiH4 during dehydrogenation, the apparent activation energy of the composite reduced to 73.2 kJ mol−1 H2 from 129.5 kJ mol−1 H2.  相似文献   

10.
A study of the effect of the ball-milling gas environment on the kinetic enhancement of MgH2 with different additives was conducted using argon and hydrogen. The as-sourced MgH2 was milled for 20 h and then milled for a further 2 h after adding 1–2 mol% of one of the additives titanium isopropoxide, niobium oxide or carbon buckyballs, varying the gas environment for both ball-milling stages. The milling environment had little or no effect on the desorption kinetics in most cases. However, in some cases, the absorption uptake differed by up to 2 wt%, depending on the gas used. This effect was not consistent among the composite samples surveyed, demonstrating the importance of reporting all information about the ball-milling processes used, including the gas environment.  相似文献   

11.
MgH2 is considered as a promising hydrogen storage material for on-board applications. In order to improve hydrogen storage properties of MgH2, the amorphous TiMgVNi3-doped MgH2 is prepared by ball milling under hydrogen atmosphere. It is found that the catalytic (Ti,V)H2 and Mg2NiH4 nanoparticles are in situ formed after activation. As a result, the amorphous TiMgVNi3-doped MgH2 exhibits enhanced dehydrogenation kinetics (the activation energy for hydrogen desorption is 94.4 kJ mol?1 H2) and superior cycle durability (the capacity retention rate is up to 92% after 50 cycles). These results demonstrate that the in situ formation of highly dispersed catalytic nanoparticles from an amorphous phase is an effective pathway to enhance hydrogen storage properties of MgH2.  相似文献   

12.
Reversible hydrogen storage in MgH2 under mild conditions is a promising way for the realization of “Hydrogen Economy”, in which the development of cheap and highly efficient catalysts is the major challenge. Herein, A two-dimensional layered Fe is prepared via a facile wet-chemical ball milling method and has been confirmed to greatly enhance the hydrogen storage performance of MgH2. Minor addition of 5 wt% Fe nanosheets to MgH2 decreases the onset desorption temperature to 182.1 °C and enables a quick release of 5.44 wt% H2 within 10 min at 300 °C. Besides, the dehydrogenated sample takes up 6 wt% H2 in 10 min under a hydrogen pressure of 3.2 MPa at 200 °C. With the doping of Fe nanosheets, the apparent activation energy of the dehydrogenation reaction for MgH2 is reduced to 40.7 ± 1.0 kJ mol−1. Further ab initio calculations reveal that the presence of Fe extends the Mg–H bond length and reduces its bond strength. We believe that this work would shed light on designing plain metal for catalysis in the area of hydrogen storage and other energy-related issues.  相似文献   

13.
Additive doping is one of the effective methods to overcome the shortcomings of MgH2 on the aspect of relatively high operating temperatures and slow desorption kinetics. In this paper, hollow g-C3N4 (TCN) tubes with a diameter of 2 μm are synthesized through the hydrothermal and high-temperature pyrolysis methods, and then nickel is chemically reduced onto TCN to form Ni/TCN composite at 278 K. Ni/TCN is then introduced into the MgH2/Mg system by means of hydriding combustion and ball milling. The MgH2–Ni/TCN composite starts to release hydrogen at 535 K, which is 116 K lower than the as-milled MgH2 (651 K). The MgH2–Ni/TCN composite absorbs 5.24 wt% H2 within 3500 s at 423 K, and takes up 3.56 wt% H2 within 3500 s, even at a temperature as low as 373 K. The apparent activation energy (Ea) of the MgH2 decreases from 161.1 to 82.6 kJ/mol by the addition of Ni/TCN. Moreover, the MgH2–Ni/TCN sample shows excellent cycle stability, with a dehydrogenation capacity retention rate of 98.0% after 10 cycles. The carbon material enhances sorption kinetics by dispersing and stabilizating MgH2. Otherwise, the phase transformation between Mg2NiH4 and Mg2NiH0.3 accelerates the re/dehydrogenation reaction of the composite.  相似文献   

14.
In this study, some transition metal sulfides (TiS2, NbS2, MoS2, MnS, CoS2 and CuS) are used as catalyst to enhance the hydrogen storage behaviors of MgH2. The MgH2-sulfide composites with different sulfides addition are prepared by ball-milling. The phase composition and hydrogen storage properties are studied in detail. The results confirm that all these sulfides can significantly increase the hydrogen desorption and absorption kinetics of MgH2. The MgH2–TiS2 has the best hydrogenation and dehydrogenation kinetics, followed by the MgH2–NbS2, MgH2–MnS, MgH2–MoS2, MgH2–CoS2, MgH2–CuS and MgH2. Also, the onset dehydrogenation temperature of the MgH2–TiS2 is about 204 °C, which is lower about 126 °C than that of the MgH2. The dehydrogenation activation energy can be reduced to 50.8 kJ mol?1 when doping TiS2 in MgH2. The beneficial catalytic effects of the sulfides can be ascribed to the in-situ formation of MgS, TiH2, NbH, Mo, Mn, Mg2CoH5 and MgCu2 phases.  相似文献   

15.
With the depletion of global energies resources, improvement of hydrogen storage properties of materials like MgH2 is of great interest for future efficient renewable resources. In this study, a novel antiperovskite MgCNi3 was synthesized by powder metallurgy then introduced into Mg to fabricate MgMgCNi3 composite. The hydrogen storage properties of the obtained MgMgCNi3 composite were evaluated. MgMgCNi3 showed a high capacity of hydrogen storage and fast kinetics of hydrogen uptake/release at relatively low temperatures. About 4.42 wt% H2 was absorbed within 20 min at 423 K, and 4.81 wt% H2 was reversibly released within 20 min at 593 K. By comparison, milled MgH2 absorbed only 0.99 wt% H2 and hardly underwent any hydrogen evolution under the same conditions. In addition, MgMgCNi3 composite showed outstanding cycling stability, with hydrogen absorption capacity retention rates reaching 98% after ten cycles at 623 K. The characterization analyses revealed that MgCNi3 and Mg formed Mg2NiH4 hydride and carbonaceous material during hydrogenation, where Mg2NiH4 induced dehydrogenation of MgH2 and carbon played a dispersive role during the composite reaction. Both features synergistically benefited the hydrogen storage properties of MgH2.  相似文献   

16.
Mg(BH4)2 is an attractive hydrogen storage material, owing to its high gravimetric capacity of 14.9 wt %. However, the dehydrogenated material MgB2 is very difficult to rehydrogenate, requiring excessive pressures and temperatures. Here we report the influence of LiH and TiH2 on hydrogen storage reactions involving Bulk MgB2 using XRD, XAS, FTIR and NMR. In ball-milled mixtures of LiH/MgB2, the LiH loses crystallinity but remains undissociated, forming a weakly bound complex with MgB2. The weak interactions produce minor variations in the local electronic structure at B and Mg, but do not markedly affect the underlying MgB2 hexagonal crystal structure. No evidence is found for a mixed-metal boride Mg1-xLixB2 in the as-prepared LiH/MgB2 materials. The presence of LiH dramatically improves the hydrogenation of MgB2 at 700 bar, forming borohydride 100 °C below the minimum hydrogenation temperature of pure MgB2 and without the formation of undesirable intermediates such as [B3H8]-, [B10H10]2- or [B12H12]2-. Evidence is reported for a mixed-metal borohydride of the type Mg(3-x)/2Lix(BH4)3 produced by the hydrogenation. Subsequent desorption is also improved compared to pure Mg(BH4)2 and LiBH4, showing single-step hydrogen release up to ~8 wt% by 380 °C, whereas Mg(BH4)2 and LiBH4 still retain significant amounts of hydrogen at this temperature. The material produced by desorption contains both MgB2 and Mg metal, revealing the original LiH/MgB2 system is not fully reversible. In contrast to LiH, TiH2 is essentially inert when ball-milled with MgB2, and high-pressure hydrogenation leaves only unreacted TiH2 and MgB2. Thus, added TiH2 provides no benefit to MgB2 hydrogenation.  相似文献   

17.
In the present investigation, we have reported the synergistic effect of Fe nanoparticles and hollow carbon spheres composite on the hydrogen storage properties of MgH2. The onset desorption temperature for MgH2 catalyzed with hollow carbon spheres and Fe nanoparticle (MgH2-Fe-HCS) system has been observed to be 225.9 °C with a hydrogen storage capacity of 5.60 wt %. It could be able to absorb 5.60 wt % hydrogen within 55 s and desorb 5.50 wt % hydrogen within 12 min under 20 atm H2 pressure at 300 °C. The desorption activation energy of MgH2-Fe-HCS has been found to be 84.9 kJ/mol, whereas the desorption activation energies for as received MgH2, Hollow carbon sphere catalyzed MgH2 and Fe catalyzed MgH2 are found to be 130 kJ/mol, 103 kJ/mol, and 94.2 kJ/mol respectively. MgH2-Fe-HCS composite lowered the change in enthalpy of hydrogen desorption from MgH2 by 20.02 kJ/mol as compared to pristine MgH2. MgH2-Fe-HCS shows better cyclability up to 24 cycles of hydrogenation and dehydrogenation of MgH2. The mechanism for the better catalytic action of Fe and HCS on MgH2 has also been discussed.  相似文献   

18.
A metal-organic framework based on Ni (II) as metal ion and trimasic acid (TMA) as organic linker was synthesized and introduced into MgH2 to prepare a Mg-(TMA-Ni MOF)-H composite through ball-milling. The microstructures, phase changes and hydrogen storage behaviors of the composite were systematically studied. It can be found that Ni ion in TMA-Ni MOF is attracted by Mg to form nano-sized Mg2Ni/Mg2NiH4 after de/rehydrogenation. The hydriding and dehydriding enthalpies of the Mg-MOF-H composite are evaluated to be −74.3 and 78.7 kJ mol−1 H2, respectively, which means that the thermodynamics of Mg remains unchanged. The absorption kinetics of the Mg-MOF-H composite is improved by showing an activation energy of 51.2 kJ mol−1 H2. The onset desorption temperature of the composite is 167.8 K lower than that of the pure MgH2 at the heating rate of 10 K/min. Such a significant enhancement on the sorption kinetic properties of the composite is attributed to the catalytic effects of the nanoscale Mg2Ni/Mg2NiH4 derived from TMA-Ni MOF by providing gateways for hydrogen diffusion during re/dehydrogenation processes.  相似文献   

19.
Mg(BH4)2 is a promising solid-state hydrogen storage material, releasing 14.9 wt% hydrogen upon conversion to MgB2. The rehydrogenation of MgB2 is particularly challenging, requiring prolonged exposure to high pressures of hydrogen at high temperature. Here we report an XPS study probing the influence of LiH and TiH2 on the hydrogen storage properties of MgB2 in the surface and near-surface regions, as a complementary investigation to a preceding study of the bulk properties. Surface and near-surface properties are important considerations for nanoscale and bulk hydrogen storage materials. If there are reactions occurring at the surface that modify the chemical composition in the near-surface region, species diffusion can alter the chemical composition even deep into the bulk of the material. For LiH/MgB2, metastable LiH–B and LiH–Mg species are produced that are more reactive than Bulk MgB2. With prolonged glovebox storage, the LiH/MgB2 material shows increased reactivity towards O and C and enriched levels of Li and B in the near-surface region. In addition, Li induces the growth of Li2CO3 in the surface and near surface regions. Exposing LiH/MgB2 to hydrogen at 700 bar and 280 °C for 24 h produces borohydride at a temperature 100 °C below the threshold for bulk MgB2 hydrogenation. In a specifically surface process with macroscopic implications, the hydrogenation conditions also cause Li2CO3 to react with boron hydroxide in the sample to form a Li-deficient glassy lithium borate melt at the interfaces of the particles, bonding them together. Subsequent heating to 380 °C dehydrogenates the borohydride and eliminates the Li-deficient glassy lithium borate. The LiH/MgB2 material is not reversible because desorption does not lead back to LiH/MgB2, but rather to elemental B and Mg metal in the near-surface region. In contrast to LiH, TiH2 does not react with MgB2, despite the favorable thermodynamics for destabilization via TiB2 formation. Furthermore, high pressure hydrogenation yields only unreacted TiH2 and MgB2 in the surface and near-surface regions. Thus, added TiH2 provides no benefit to MgB2 hydrogenation, in agreement with the findings of the preceding bulk study.  相似文献   

20.
The influence of CuFe2O4 addition on the sorption performances of MgH2 prepared by ball milling was studied for the first time. The MgH2 + 10 wt% CuFe2O4 sample exhibited an enhancement in hydrogen storage performance compared to that of as-milled MgH2, with the onset decomposition temperature decreased from 340 °C to 250 °C. Dehydrogenation kinetic result revealed that CuFe2O4-added MgH2 released around 5.3 wt% H2 within 10 min at 320 °C, while the as-milled MgH2 released below 1.0 wt% H2 under the same condition. Furthermore, about 5.0 wt% H2 was absorbed at 250 °C in 30 min for the 10 wt% CuFe2O4-doped MgH2 sample. In contrast, the un-doped MgH2 only absorbed 4.0 wt% H2 at 250 °C in 30 min. From the Kissinger analysis, the apparent activation energy of as-milled MgH2 was 166.0 kJ/mol and this value decreased to 113.0 kJ/mol for 10 wt% CuFe2O4-added MgH2. The enhanced sorption performance of MgH2 in the presence of CuFe2O4 is believed to be due to the role of in situ formed Fe, Mg-Cu alloy, and MgO phases as an active species to catalyse the hydrogen storage properties of MgH2.  相似文献   

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