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1.
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 The impact of another hydride nickel precursor in which chloride has been replaced by a borohydride ligand, namely NiH(BH4)(P(C6H11)3)2, is also reported.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   

2.
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   

3.
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   

4.
Element substitution is an effective strategy for improving Mg-based alloys in their hydrogenation/dehydrogenation property. Thereby, in this paper, Sm was selected to partially replace La in a La–Mg-based alloy for improving its hydriding and dehydriding performance. The alloys with the compositions of Mg80Ni10La10-xSmx (x = 0–4) were manufactured through vacuum induction melting. Their microstructures and phase compositions were measured by XRD, SEM and HRTEM. The isothermal hydrogen storage property was tested through an automatic Sieverts apparatus. Non-isothermal hydrogen desorption performance was measured through TGA and DSC. Arrhenius and Kissinger methods were adopted to calculate the dehydrogenation activation energy of alloys. The results reveal that all of the experimental alloys can reversibly absorb and release a large amount of H2 at appropriate temperatures. The substitution of Sm for La ameliorates the hydriding and dehydriding kinetics, but it results in an undesired reduction of hydrogen absorption and desorption capacities. Substituting La by Sm decreases the initial hydrogen release temperature of the hydride visibly. Furthermore, substituting Sm for La engenders the dehydrogenation activation energy decline clearly, which is considered as the main reason for the improved hydrogen desorption kinetics resulted from Sm replacing La.  相似文献   

5.
Mg2In0.1Ni solid solution with an Mg2Ni-type structure has been synthesized and its hydrogen storage properties have been investigated. The results showed that the introduction of In into Mg2Ni not only significantly improved the dehydrogenation kinetics but also greatly lowered the thermodynamic stability. The dehydrogenation activation energy (Ea) and enthalpy change (ΔH) decreased from 80 kJ/mol and 64.5 kJ/mol H2 to 28.9 kJ/mol and 38.4 kJ/mol H2, respectively. The obtained results point to a method for improving not only the thermodynamic but also the kinetic properties of hydrogen storage materials.  相似文献   

6.
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   

7.
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   

8.
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   

9.
Mg-based hydrogen storage alloys have become a research hotspot in recent years owing to their high hydrogen storage capacity, good reversibility of hydrogen absorption/desorption, low cost, and abundant resources. However, its high thermodynamic stability and slow kinetics limit its application, so the modification of Mg-based hydrogen storage alloys has become the development direction of Mg-based alloys. Transition metals can be used as catalysts for the dehydrogenation of hydrogen storage alloys due to their excellent structural, electrical, and magnetic properties. Graphene, because of its unique sp2 hybrid structure, excellent chemical stability, and a specific surface area of up to 2600 m2/g, can be used as a support for transition metal catalysts. In this paper, the internal mechanism of graphene as a catalyst for the catalysis of Mg-based hydrogen storage alloys was analyzed, and the hydrogen storage properties of graphene-catalyzed Mg-based hydrogen storage alloys were reviewed. The effects of graphene-supported different catalysts (transition metal, transition metal oxides, and transition metal compounds) on the hydrogen storage properties of Mg-based hydrogen storage alloys were also reviewed. The results showed that graphene played the roles of catalysis, co-catalysis, and inhibition of grain aggregation and growth in Mg-based hydrogen storage materials.  相似文献   

10.
The Y1-xMgxNi2.1 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5) alloys were prepared by sintering method in this work. The effect of Mg on structural transformation, hydrogen storage properties, and structural stability were investigated. It is found that with the increase of Mg substitution the abundance of (Y, Mg)Ni2 phase increases and the total amount of (Y, Mg)Ni3 and (Y, Mg)2Ni7 phases first increases and then decreases. Mg preferentially enters into the (Y, Mg)Ni2 phase. When the Mg content in (Y, Mg)Ni2 phase is higher than 0.2, the (Y, Mg)Ni2 phase forms and does not undergo hydrogen induced amorphization and disproportionation. The hydrogen storage capacity decreases owing to the transformation from (Y, Mg)Ni2 phase to the more stable (Y, Mg)Ni3 phase. When the Mg content in (Y, Mg)Ni2 phase increases to 0.5, the atomic radius ratio of A-side to B-side reduces to less than 1.37, there is no capacity attenuation after 50 cycles.  相似文献   

11.
Structural, hydrogen storage, and electrochemical properties of LaMgNi4 alloy were investigated in this study to determine whether it can be used as an active material of the negative electrode in nickel–metal hydride (Ni/MH) batteries. X-ray diffraction study showed that amorphization occurs at the first dehydrogenation cycle and was recovered crystallization after 873 K annealing.Maximum hydrogen storage capacity reached 1.4 wt% in the first hydrogenation under 373 K. The reannealed alloy showed improved reversible hydrogen storage capacity at ~0.9 wt% due to more LaNi5 phase composition. Electrodes prepared from the investigated alloy showed maximum discharge capacities of ~340 mAh/g at 10 mA/g. The LaMgNi4 alloy electrode exhibited satisfactory cycling stability remaining 47% of its initial capacity after 250 cycles. The negative cohesive energy indicated the exothermic process and stable compound structures of the LaMgNi4 alloy and its hydrides via Density functional theory calculations.  相似文献   

12.
A novel embedded Mg-based hydrogen storage nanocomposite was prepared by mechanical milling of hydriding combustion synthesized (HCS) Mg-based hydride and hydrogen permissive/oxygen prohibitive polymer. The Mg-based hydride was mechanically milled with tetrahydrofuran solution of polymethyl methacrylate (PMMA) under argon atmosphere. It is determined by X-ray diffraction (XRD) analysis that the average grain size of all the milled nanocomposites become smaller and the nanocomposites exhibit a good air-stable property. The microstructures of the nanocomposites obtained by Field emission scanning electron microscopy (FESEM) and High-resolution transmission electron microscopy (HRTEM) analyses show that Mg95Ni5 particles embedded by PMMA have a diameter of smaller than 100 nm, approximately. The nanocomposites show the optimal hydriding/dehydriding properties, requiring 60 min to absorb 3.37 wt.% hydrogen at low temperature of 473 K, and desorbing as high as 1.02 wt.% hydrogen within 120 min at the same temperature. The onset dehydriding temperature of the composites is about 373 K, which is 150 K lower than that of HCS products Mg95Ni5.  相似文献   

13.
On the basis of modification of transition metals on Mg-Al hydrogen storage alloys, Mg15Al5Ni alloy with Ni content of 5 wt% has been prepared by high energy ball mill. The results show that Ni particles uniformly distribute on the surface of particles, while several Ni particles are embedded inside alloy particles. These Ni particles tend to redistribute after hydrogenation. The phase composition analysis reveals the formation of stable Al3Ni2 phase in Ni-modified alloy after hydrogenation. The hydrogen absorption performance of Mg15Al5Ni alloy has been improved by introducing Ni, which can absorb 4.36 wt% hydrogen within 5 min at 350 °C. Meanwhile, the activation properties of Mg15Al5Ni alloy can be obviously deteriorated due to the addition of Ni. However, uniformly distributed Al3Ni2 nanocrystals with grain sizes around 10 nm hinder grain growth of hydrides, ameliorating hydrogenation kinetics of Mg15Al5Ni alloy. Besides, the modified effect of Ni on hydrogenation kinetics of Mg15Al5Ni alloy has been also discussed in this work.  相似文献   

14.
Ternary Mg86Y10Ni4 alloy was successfully prepared by vacuum induction melting and subsequent melt-spinning technique. The phase composition and microstructure of the melt-spun and hydrogenated samples were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy measurements. The melt-spun alloy had an amorphous structure, and it transformed into nanocrystalline during the first hydrogenation process. The hydrogenated sample was composed of MgH2, Mg2NiH4, YH2, and a small amount of YH3. The hydrogen absorption/desorption kinetics and thermodynamics were measured by Sievert's apparatus at various temperatures. It was found that the melt-spun Mg86Y10Ni4 alloy could be fully activated after five hydrogenation and dehydrogenation cycles at 380 °C, and it exhibited a reversible gravimetric hydrogen storage capacity of about 5.3 wt%. The enhanced hydrogen sorption kinetics during the first few cycles can be attributed to the increased specific surface caused by the pulverization and cracking of the alloy particles. The activation energy for dehydrogenation reaction was determined to be 67 kJ/mol and 71 kJ/mol by using Arrhenius equation and Kissinger equation respectively. The thermodynamics of the sample was also evaluated by pressure–composition–isotherms, and the results shown that the enthalpy and entropy changes of Mg/MgH2 transformation in the Mg86Y10Ni4 alloy were slightly higher than that of pure Mg/MgH2.  相似文献   

15.
The effects of annealing at 1123, 1148, 1173 and 1198 K for 16 h on the structure and properties of the LaY2Ni10Mn0.5 hydrogen storage alloy as the active material of the negative electrode in nickel–metal hydride (Ni–MH) batteries were systematically investigated by X-ray diffraction (XRD), scanning electron microscopy linked with an energy dispersive X-ray spectrometer (SEM–EDS), pressure-composition isotherms (PCI) and electrochemical measurements. The quenched and annealed LaY2Ni10Mn0.5 alloys primarily consist of Ce2Ni7- (2H) and Gd2Co7-type (3R) phases. The homogeneity of the composition and plateau characteristics of the annealed alloys are significantly improved, and the lattice strain is effectively reduced. The alloys annealed at 1148 K and 1173 K have distinctly greater hydrogen storage amounts, 1.49 wt% (corresponding to 399 mAh g?1 in equivalent electrochemical units) and 1.48 wt%, respectively, than the quenched alloy (1.25 wt%, corresponding to 335 mAh g?1 in equivalent electrochemical units). The alloys annealed at 1148 K and 1173 K have relatively good activation capabilities. The annealing treatment slightly decreases the discharge potentials of the alloy electrodes but markedly increases their discharge capacity. The maximum discharge capacities of the annealed alloy electrodes (372–391 mAh g?1) are greater than the extreme capacity of the LaNi5-type alloy (370 mAh g?1). The cycling stability of the annealed alloy electrodes was improved.  相似文献   

16.
Spark plasma sintering (SPS) is a newly developed material preparation technology and is very suitable for the multi-component and/or dissimilar materials preparation. In this paper, Mg–V77.8Zr7.4Ti7.4Ni7.4, Mg–V38Zr25Ti15Ni22 and Mg–ZrMn2 composites were synthesized by SPS method and their hydrogen storage properties were evaluated. The results showed that with the addition of the second alloys, the hydrogen desorption temperature of pure Mg decreased apparently, with the reversible hydrogen storage capacity increased from nearly 0 of pure Mg to near 95% of its total absorption at 573 K. The hydrogen ab/desorption kinetics were also greatly improved, with the hydrogen absorption mechanism changed from surface reaction of pure Mg to three-dimension diffusion of the composite. TEM observation indicated that a thin transition zone of nanocrystalline Mg was produced at the sintering interface during SPS, which may be responsible for the improvement of hydrogen storage properties of these Mg-based composites.  相似文献   

17.
The structure and electrochemical properties of titanium-based hydrogen storage alloy prepared by solid phase sintering at 1123 K were investigated. The result of X-ray diffraction (XRD) showed that the sintered alloy mainly consists of Ti2Ni phase coexisting with TiNi, TiNi3 and Ni phases. The alloy had a maximum discharge capacity of 205 mAh/g at a discharge current density of 60 mA/g and showed a discharge capacity of 146 mAh/g at 150 mA/g. The results of linear polarization (LP) and potential-step measurement presented that the exchange current density and hydrogen diffusion efficient of the alloy were 100 mA/g and 4.2 × 10−9 cm2/s, respectively. The electrochemical performance of the alloy could be effectively improved by using solid phase sintering.  相似文献   

18.
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   

19.
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   

20.
The feasibility of scaling up the production of a Mg-based hydride as material for solid state hydrogen storage is demonstrated in the present work. Magnesium hydride, added with a Zr–Ni alloy as catalyst, was treated in an attritor-type ball mill, suitable to process a quantity of 0.5–1 kg of material. SEM–EDS examination showed that after milling the catalyst was well distributed among the magnesium hydride crystallites. Thermodynamic and kinetic properties determined by a Sievert's type apparatus showed that the semi-industrial product kept the main properties of the material prepared at the laboratory scale. The maximum amount of stored hydrogen reached values between 5.3 and 5.6 wt% and the hydriding and dehydriding times were of the order of few minutes at about 300 °C.  相似文献   

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