Improvement on hydrogen storage thermodynamics and kinetics of the as-milled SmMg11Ni alloy by adding MoS2

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.     

Thermodynamics and reaction pathways of hydrogen sorption in Mg6(Pd,TM) (TM = Ag,Cu and Ni) pseudo-binary compounds

Mg₆(Pd,TM) (TM = Ag, Cu and Ni) pseudo-binary compounds have been synthesized at the TM solubility limit to determine the influence of TM on the thermodynamics and reaction pathways of the Mg₆Pd–H system. All compounds exhibit a two-plateau pressure behaviour, being the value of the high plateau pressure well above that of the Mg/MgH₂ system. Such destabilization is explained by the formation of different Mg–(Pd,TM) intermetallics and/or Mg₂NiH₄ hydride phases during the hydrogenation reaction. The formation of these phases not only increases the enthalpy of hydrogenation but also enhances disorder leading to a limited destabilization of the hydrogenated state. This compensation effect is characterized by a linear correlation between enthalpy and entropy terms. In addition, this work also provides the assessment at 623 K of the ternary Mg–Pd–Cu phase diagram in the Mg-rich corner.     

Tunable microstructure,de-/hydrogenation kinetics and thermodynamics performance of Mg–Ni–La–Ti–H systems

In the light of positive effects of rare earth and transition metals on the hydrogen absorption/desorption properties of magnesium, the Mg20La–5TiH₂, Mg20Ni–5TiH₂ and Mg10Ni10La–5TiH₂ composites have been prepared in this work to ameliorate the de-/hydrogenation kinetics and thermodynamic performance. The results indicate that the as-prepared composites are mainly composed of Mg, Mg₂Ni/LaH₃ and TiH₂ phases after activation, and LaH₃ and TiH₂ are stable during de-/hydrogenation cycles. The morphology observations give evidences that LaH₃ with size about ~20 nm and Mg₂Ni with size about ~1 μm are uniformly distributed in the composites. It is noted that the de-/hydriding kinetics of the as-prepared composites are significantly improved after internal and surface modification, of which the Mg10Ni10La–5TiH₂ composite can desorb as high as 5.66 wt% hydrogen within 3 min at 623 K. Moreover, the thermodynamic properties of the experimental composites have also been investigated and discussed according to the pressure-composition isothermal curves and corresponding calculation by Van't Hoff equation. The improved hydrogen storage properties of the as-prepared composites are mainly attributed to the uniformly distributed LaH₃, Mg₂Ni and TiH₂ phases, which provide a large amount of phase boundaries, diffusion paths and nucleation sites for de-/hydrogenation reactions.     

Hydrogen absorption properties of Zr(V1−xFex)2 intermetallic compounds

The Zr(V_1−xFe_x)₂ (x = 0.02, 0.05, 0.10, 0.15, 0.25) alloys were prepared by the arc-melt method and annealed at 1273 K for 168 h in an argon atmosphere. Phase structure investigations of the as-cast and annealed Zr(V_1−xFe_x)₂ alloys indicate the annealing treatment can eliminate the minority phases originating from the non-equilibrium solidification of as-cast alloys. The ZrV₂-type phase becomes the dominant one in each annealed alloy. The substitution of Fe in V sites leads to the contraction of their lattice. For annealed Zr(V_1−xFe_x)₂ alloys, the P–t and PCT curves obtained between 673 K and 823 K give the evidence that the absorption process is controlled by a rate-controlling hydrogen diffusion. With the increase of iron, the equilibrium pressure and the plateau slope increase while the hydrogenation capacity and the absolute value of enthalpy and entropy decrease accordingly. The stability of metal hydride reduces gradually as the Fe content varies from x = 0.02 to 0.25 which promotes the hydrogen release and favors the practical applications of the Zr(V_1−xFe_x)₂ alloys.     

Hydrogen storage property improvement of La–Y–Mg–Ni alloy by ball milling with TiF3

Ball milling the powders of Mg-based alloys with transition metal compounds is effective for improving their hydrogen storage performances. In this experiment, the alloys of La_1.7Y_0.3Mg₁₆Ni + x wt.% TiF₃ (x = 0–10) were prepared through mechanical milling technology. XRD, SEM, HRTEM and granulometry were used to measure the composition and microstructure of alloys. The isothermal hydrogen storage property was measured by a Sievert apparatus. The results reveal that the TiF₃ additive in ball-milled samples transforms into MgF₂ and TiH₂ after the first hydrogen absorption. Adding TiF₃ enhances the crystallinity and reduces the average particle and crystallite sizes of alloys, which is beneficial to accelerating hydriding and dehydriding kinetics. Adding 7 wt% TiF₃ into alloy decreases the dehydrogenation activation energy from 72.2 to 64.0 kJ/mol and improves the hydrogen absorption rate at low temperatures, absorbing 3.50 wt% H in 0.5 min at 323 K.     

Hydrogen storage thermodynamics and kinetics of RE–Mg–Ni-based alloys prepared by mechanical milling

The nanocrystalline/amorphous NdMg₁₁Ni + x wt.% Ni (x = 100, 200) composite hydrogen storage alloys were synthesized by ball milling, and the effects of Ni content and milling time on the hydrogen storage thermodynamics and dynamics of the alloys were systematically investigated. The results reveal that the variation of the Ni content has a slight effect on the thermodynamic properties of the alloys, but it significantly improves their absorption and desorption kinetics performance. The variation of the milling time clearly affects the hydrogen storage properties of the alloys. Hydrogen absorption capacity and hydrogen absorption saturation ratio have maximum values with milling time varying. But hydrogen desorption ratio always increases with milling time prolonging. It is found that the hydrogen desorption activation energy of the alloys clearly decreases with increasing Ni content and milling time, which is responsible for the improved hydrogen desorption kinetics of the alloys.     

Improved hydrogen storage kinetics of nanocrystalline and amorphous Pr-Mg-Ni-based PrMg12-type alloys synthesized by mechanical milling

In this paper, the nanocrystalline and amorphous PrMg₁₁Ni + x wt.% Ni (x = 100, 200) alloys were synthesized by mechanical milling. The gaseous and electrochemical hydrogen storage performances were studied in detail. The results reveal that increasing Ni content facilitates the glass forming of the alloys, and it significantly improves the gaseous and electrochemical hydrogen storage kinetics performance. Furthermore, milling time varying significantly affects the hydrogen storage properties of the alloys. The hydrogen capacity of the alloys first increases and then decreases with milling time prolonged. The hydriding rate and high-rate discharge ability (HRD) of the as-milled alloys have maximum values with milling time varying. But dehydriding rate always increases with milling time prolonged. The improved gaseous hydrogen storage kinetics of alloys are convinced to be ascribed to a reduction in hydrogen desorption activation energy caused by increasing Ni content and prolonging milling time.     

Hydrogen storage characteristics of magnesium impregnated on the porous channels of activated charcoal scaffold

Ball milled (30 h) MgH₂ is impregnated on the pores/grooves of activated charcoal scaffold using a programmed heat treatment at 550 °C under 5 bar pure hydrogen ambient. The result obtained by this approach is better and more consistent than the materials prepared by metal infiltration at 650 °C or vacuum heated samples under 550 °C. The activation energy value (88 kJ/mol) obtained in the case of impregnated catalyst free material is far better than the activation energy value of the unconfined material (149 kJ/mol). The impregnated material can absorb hydrogen almost closer to its actual capacity at ∼1 bar under 170 °C. The low temperature desorption characteristics and ab/desorption behaviors are extensively analyzed and described.     

Effect of nano-structured Ta2C on hydrogen absorption−desorption kinetics of Mg−H2 system

High purity Ta₂C was successfully prepared and the hydrogen absorption−desorption kinetic properties of MgH₂−10 wt% Ta₂C composites were investigated systematically. It was found that the hydrogen absorption of Mg−10 wt% Ta₂C (20 nm) composite takes about 5 min to reach saturation at 573 K, and its hydride fully desorbs hydrogen within 15 min at 623 K. These kinetic properties are much better than those of the undoped Mg and MgH₂ prepared under the same condition, respectively. The improvement in the hydrogen storage kinetics is ascribed to the catalytic effect of Ta₂C and its inhibition role in crystallite growth.     

Effect of annealing on microstructure and hydrogenation properties of TiFe + X wt% Zr (X = 4, 8)

The effect of annealing on the hydrogenation characteristics of the TiFe alloy was investigated. Pellets of TiFe + X wt% Zr (X = 4, 8) were synthesized by arc melting, using industrial grade Fe (ASTM 10005) and Ti (ASTM B265 grade 1) and annealed at 1173 K for 24 h under argon atmosphere. Crystal structure and lattice parameters were determined by X-ray diffraction (XRD) pattern. Scanning electron microscopy (SEM) image of these alloys showed important differences in the microstructure before and after annealing. The main effect of annealing was to reduce the scale of the secondary phase. Change of composition for the TiFe phase and the secondary phases was relatively limited. Despite the relatively minor changes in crystal structures, the first hydrogenation kinetics was much slower and hydrogen capacity smaller for annealed samples compared to their as-cast counterparts. The mechanism responsible for the degradation of hydrogenation kinetics is still unclear but it may be due to modification in the chemical composition of the interface between the TiFe phase and the secondary phase.     

Effect of La partial substitution for Zr on the Structural and electrochemical properties of Ti0.17Zr0.08-xLaxV0.35Cr0.1Ni0.3 (x = 0–0.04) electrode alloys

In order to elucidate the effects of metallic La addition on the performance of Ti–V-based hydrogen storage alloys as negative electrodes for nickel/metal-hydrides batteries, Ti_0.17Zr_0.08-xLa_xV_0.35Cr_0.1Ni_0.3 (x = 0, 0.01, 0.02, 0.03, 0.04) alloys were prepared and their structural and electrochemical properties were systematically investigated. X-ray powder diffraction (XRD) results showed that these alloys were mainly consisted of C14 Laves phase with a hexagonal structure, V-based solid solution phase with BCC structure and C15 Laves phase with a cubic structure. The electrochemical measurements indicated that the maximum discharge capacities of the alloy electrodes decreased from 337.3 mAh/g (x = 0) to 262.5 mAh/g (x = 0.04) and that the substitution of Zr with metallic La in the alloys had no obvious effect on the capacity retention rate (C₁₀₀/C_max, C₂₀₀/C_max). The high-rate dischargeability (HRD) of the alloy electrodes at the discharge current density of 800 mA/g first increased from 69.01% (x = 0) to 71.13% (x = 0.01) and then decreased to 65.35% (x = 0.04). In brief, the HRD was improved with an optimum La content in the alloy (x = 0.01). The electrochemical hydrogen kinetics of the alloy electrodes was further studied by means of electrochemical impedance spectroscopy, linear polarization, anodic polarization and potential-step measurements. The charge-transfer reaction resistance R_ct decreased for x = 0.01 with respect to x = 0 and then increased with the increase of x, while exchange current density I₀, limiting current density I_L and hydrogen diffusion coefficient D were all increased for x = 0.01 with respect to x = 0 and then decreased with the increase of x. The optimal content of La in Ti_0.17Zr_0.08-xLa_xV_0.35Cr_0.1Ni_0.3 alloys for negative electrodes in alkaline rechargeable secondary batteries is x = 0.01 in this study.     

Hydrogen storage properties of Mg–Ce–Ni nanocomposite induced from amorphous precursor with the highest Mg content

The effect of Ce and Ni contents on the glass-forming ability (GFA) of Mg–Ce–Ni system in the Mg-rich corner of Mg–Ce–Ni system is revealed. Ce is more advantageous for the GFA of Mg-rich Mg–Ce–Ni system than Ni, and the lowest Ce content is ∼5 at.% to obtain the fully amorphous alloy. Amorphous alloy with the highest Mg content, Mg₉₀Ce₅Ni₅, was obtained by melt-spinning. With the amorphous alloy as precursor, nanostructure multi-phases compositae was prepared by crystallizing it in hydrogenation process. The compositae with reversible hydrogen storage capacity of 5.3 wt.% shows much faster kinetics and lower MgH₂ desorption activation energy than those of induction-melt Mg₉₀Ce₅Ni₅ alloy. Both in situ formed nanosized Mg₂Ni and CeH_2.73 act as effective catalysts and significantly improve the hydrogen storage properties of MgH₂.     

Electrochemical hydrogen storage properties of Mg2−xAlxNi (x = 0, 0.3, 0.5, 0.7) prepared by hydriding combustion synthesis and mechanical milling

Mg_2−xAl_xNi (x = 0, 0.3, 0.5, 0.7) hydrogen storage alloys used as the negative electrode in a nickel–metal hydride (Ni–MH) battery were successfully prepared by means of hydriding combustion synthesis (HCS) and the selected alloy Mg_1.5Al_0.5Ni was further modified by mechanical milling (MM). The structural and electrochemical hydrogen storage properties of Mg_2−xAl_xNi alloys have been investigated in detail. XRD results show that a new phase Mg₃AlNi₂ that possesses an excellent cycling stability is observed with the substitution of Al for Mg. A short-time mechanical milling has a significant effect on improving the discharge capacity of the HCS product of Mg_1.5Al_0.5Ni. The maximum discharge capacity of Mg_1.5Al_0.5Ni ascends with increasing mechanical milling time and reaches the maximum 245.5 mAh/g when milled for 10 h. The alloy milled for 5 h shows the best electrochemical kinetics, which is due to its smaller mean particle size and uniform distribution of the particles. Further increasing in mechanical milling time could not bring about better electrochemical kinetics, which might be attributed to the agglomeration of the alloy particles and thus the charge-transfer reaction and hydrogen diffusion are restrained. It is suggested that the novel method of HCS + MM is promising to prepare ternary Mg-based intermetallic compound for electrochemical hydrogen storage.     

Air exposure improving hydrogen desorption behavior of Mg–Ni-based hydrides

It is well established that H₂O and O₂ have an inauspicious influence on hydrogen reactivity of hydrogen storage alloys. In this work, an unexpected improvement of the desorption behavior was discovered by just exposing the magnesium rich Mg–Ni hydrides into the air for a certain period. Upon an exposure duration of 4 months, the dehydrogenation peak and onset temperature were sharply lowered by 150 °C and 130 °C. Furthermore, the air-exposed sample could quickly absorb 3.08 wt% H₂ and desorb 2.81 wt% H₂ within 400 s at 300 °C. Besides the refinement of the powders due to the spontaneous hydrolysis reaction, the in-situ formed magnesium hydroxide layer and Ni are thought to be responsible for the remarkable improvement. This work gives interesting insights that the self-generating surface passivation is not necessarily harmful in the solid-state hydrogen storage area, especially for the cases where active sites of catalysis are present.