Effects of Mo substitution on the kinetic and thermodynamic characteristics of ZrCo1-xMox (x = 0–0.2) alloys for hydrogen storage

In this study, ZrCo_1-xMo_x (x = 0, 0.05, 0.1, 0.15, 0.2) alloys were prepared via vacuum arc-melting method. The effects of substituting Co with Mo on the structure, initial activation behaviors, and thermodynamic properties of the afore-mentioned alloys were systematically investigated. The results showed that ZrCo_1-xMo_x (x = 0, 0.05, 0.1, 0.15) alloys exhibited a single ZrCo phase and their corresponding hydrides, a ZrCoH₃ phase. Furthermore, ZrCo_0.8Mo_0.2 alloy consisted of ZrCo phase and a trace of ZrMo₂ phase, and the hydride contained ZrCoH₃ and ZrH phases. As the Mo content was increased, the initial activation period decreased significantly from 19277 s for ZrCo to 576 s for ZrCo_0.8Mo_0.2, which was closely related to the catalytic effect of ZrMo₂. The plateau width of pressure composition temperature curves were shortened, and the equilibrium pressures of hydrogen desorption decreased slightly as Mo content increased. Additionally, the experiments showed that the anti-disproportionation performance was greatly improved by Mo substitution. The extent of disproportionation decreased from 64.28% for ZrCo to 24.11% for ZrCo_0.8Mo_0.2. The positive effect of Mo substitution on improving the anti-disproportionation property of ZrCo alloy was attributed to the reduction of hydrogen atom in 8f₂ and 8e sites, which decreased the driving force of the disproportionation reaction.     

Effect of rare earth elements on electrochemical properties of La–Mg–Ni-based hydrogen storage alloys

La_0.60R_0.20Mg_0.20(NiCoMnAl)_3.5 (R = La, Ce, Pr, Nd) alloys were prepared by inductive melting. Variations in phase structure and electrochemical properties due to partial replacement of La by Ce, Pr and Nd, were investigated. The alloys consist mainly of LaNi₅ phase, La₂Ni₇ phase and LaNi₃ phase as explored by XRD and SEM. The maximum discharge capacity decreases with Ce, Pr and Nd substitution for La. However, the cycling stability is improved by substituting Pr and Nd at La sites, capacity retention rate at the 100th cycle increases by 13.4% for the Nd-substituted alloy. The electrochemical kinetics measurements show that Ce and Pr substitution improves kinetics and thus ameliorates the high rate dischargeability (HRD) and low temperature dischargeability. The HRD at 1200 mA g⁻¹ increases from 22.1% to 61.3% and the capacity at 233 K mounts up from 90 mAh g⁻¹ to 220 mAh g⁻¹ for the Ce-substituted alloy.     

Effect of carbon coating on the electrochemical properties of La–Y–Ni-based hydrogen storage alloys

The A₂B₇-type (LaSmY) (NiMnAl)_3.5 alloys were prepared by induction melting, and then the alloy samples coated with different contents of nano-carbon were prepared by the mixing and sintering method using pitch as carbon source. The effects of the contents and structure of the coated-carbon on the electrochemical properties of alloy samples were investigated. With the carbon content increase from 0.1 to 1.0 wt%, the cyclic stability is improved and the high-rate dischargeabilitiy (HRD) of the alloy electrodes first increase and then decrease. The kinetic results show that the carbon coating improves the electrocatalytic activity and electrical conductivity of the alloy electrodes. The alloy electrode with 0.5 wt% carbon coating exhibits the best electrochemical properties. The maximum discharge capacity (C_max) is 345.7 mAh·g⁻¹, the HRD₁₂₀₀ is 72.49%, and the capacity retention rate (S₃₀₀) is 79.44%.     

Structure and electrochemical hydrogen storage properties of A2B-type Ti–Zr–Ni alloys

Elemental substitution of part Ti by Zr has been carried out for Ti₂Ni alloy to form Ti_2−xZr_xNi (x = 0, 0.2, 0.4) alloys. Mechanical milling and subsequent heat treatment have been used to prepare non-equilibrium Ti–Zr–Ni alloys. The effects of Zr addition on the structure and discharge properties of Ti₂Ni alloy were investigated. The addition of Zr could enhance the discharge capacity of the non-equilibrium Ti₂Ni alloy at electrolyte temperatures of 313 and 333 K. For instance, the non-equlibrium Ti_1.6Zr_0.4Ni alloy had a stable discharge capacity of about 210 mAh/g at 313 K. However, the protective surface layer formed during heat treatment was destroyed at a high electrolyte temperature of 333 K, and thus a severe capacity loss during cycling.     

Microstructure and hydrogen storage properties of (Ti0.32Cr0.43V0.25) + x wt% La (x = 0–10) alloys

The composite alloy of Ti_0.32Cr_0.43V_0.25 with x wt% La (where x = 0–10) was prepared by arc melting technique. The effect on hydrogen storage capacity, flatness of the plateau pressure, and residual hydrogen was investigated in La added Ti_0.32Cr_0.43V_0.25. Crystalline phase and microstructure of the prepared composite alloy were investigated and characterized by XRD, SEM and TEM. The crystal structure was refinement using Rietveld analysis. The effective hydrogen storage capacity of the composite alloy was found comparable to the parent alloy, when 5 wt% La was added. The effective hydrogen capacity (∼2.31 wt%) was close to that of the parent alloy (2.35 wt%) and the plateau slope was significantly improved from 30.5 of the parent alloy to 14.6. Appropriate mechanisms associated with the improved flatness by the La addition has been discussed in terms of the refined crystalline structure. Using TG/DTA method we have shown the differences in the interaction of residual hydrogen with the BCC phase of both parent alloy and 5 wt % La mixed alloy.     

Structures and properties of Mg–La–Ni ternary hydrogen storage alloys by microwave-assisted activation synthesis

It is a challenge to prepare a material meeting two conflicting criteria – absorbing hydrogen strongly enough to reach a stable thermodynamic state and desorbing hydrogen at moderate temperature with a fast reaction rate. With the guide of the Mg–La–Ni phase diagram, microwave sintering (MS) was successfully applied to preparing Mg–La–Ni ternary hydrogen storage alloys from the powder mixture of Mg, La and Ni. Their phase structures, morphologies and hydrogen absorption and desorption (A/D) properties have been studied by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), pressure-composition-isotherm (PCI) and differential scanning calorimetry (DSC). The metal hydride of 70 Mg–9.72 La–20.28 Ni (wt pct) has the best comprehensive hydriding and dehydriding (H/D) properties, which can absorb 4.1 wt.% H₂ in 600 s and desorb 3.9 wt.% H₂ in 1500 s at 573 K. The DSC results reveal its onset temperatures of hydrogen A/D are the lowest among all the samples, which are 671.4 and 600.9 K. Its activation energy of dehydriding reaction is 113.5 kJ/mol H₂, which is the smallest among all the samples. Also, Chou model was used to analyze the reaction kinetic mechanism.     

Electrochemical hydriding of Mg–Ni–Mm (Mm = mischmetal) alloys as an effective method for hydrogen storage

In this work, the electrochemical hydriding method was used for storing hydrogen in four binary Mg–Ni (Ni content from 15 to 34 wt.%) alloys and one ternary Mg–26Ni–12Mm alloy. Both the as-cast and powdered alloys were hydrided in a 6 M KOH solution at 80 °C for 120–480 min. The structures and phase compositions of the alloys, both before and after hydriding, were studied using optical and scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction. Differential scanning calorimetry and mass spectrometry were used to study the dehydriding process. In the case of as-cast alloys, the best combination of hydriding parameters (maximum hydrogen concentration on surface; depth of hydrogen penetration) was achieved in the Mg–26Ni alloy. In the case of powdered alloys, the Mg–34Ni alloy absorbed the highest amount of hydrogen, nearly 4.5 wt.%. The only hydride formed during hydriding was the MgH₂ hydride. The results of the mass spectrometry analysis reveal a significant thermodynamic destabilization of magnesium hydride due to Ni and Mm. The decomposition temperature of MgH₂ was reduced by more than 200 °C. The results are discussed in relation to the electronic structure and atomic size of the alloying elements and the structural variations in the alloys.     

Effect of Mo–Ni treatment on electrochemical kinetics of La–Mg–Ni-based hydrogen storage alloys

In order to improve kinetic properties of La–Mg–Ni-based hydrogen storage alloys, Mo–Ni treatment was applied to La_0.88Mg_0.12Ni_2.95Mn_0.10Co_0.55Al_0.10 alloy powders. FESEM results showed that after Mo–Ni treatment some network-shaped substance with nano-size formed on the surface of the alloy particles. The EDS results revealed increase in Ni content and emerge of Mo element. EIS and Linear polarization showed that charge-transfer resistance decreased and exchange current density increased for the treated alloy electrode, and the high rate dischargeability (HRD) was consequently improved. HRD at 1500 mA/g increased from 22.5% to 39.5%. Mo- and Ni-single treatments were performed compared with the Mo–Ni treatment, and the results showed that the single treatment improved HRD slightly, far less than the Mo–Ni treatment.     

Structure and electrochemical properties of (La1−xDyx)0.8Mg0.2Ni3.4Al0.1 (x = 0.0–0.20) hydrogen storage alloys

The structure and electrochemical characteristics of (La_1−xDy_x)_0.8Mg_0.2Ni_3.4Al_0.1 (x = 0–0.20) hydrogen storage alloys have been investigated. Dysprosium was adopted as a partial substitution element for lanthanum in order to improve electrochemical properties. The XRD, SEM and EDX results showed that the alloys were composed of (La, Mg)₂Ni₇, LaNi₅ and (La, Mg)Ni₂ phases. The introduction of Dy promoted the formation of (La, Mg)₂Ni₇ phase which possesses high hydrogen storage capacity, and controlling dysprosium content at 0.05 can obtain the maximum (La, Mg)₂Ni₇ phase abundance in the alloys. The maximum discharge capacity was heightened from 382.5 to 390.2 mAh/g, which was ascribed to (La, Mg)₂Ni₇ phase abundance increasing from 54.8% to a maximum (60.5%). Also, the biggest discharge capacity retention remained 82.7% after 100 cycles at discharge current density of 300 mA/g.     

Microstructure characteristics,hydrogen storage thermodynamic and kinetic properties of Mg–Ni–Y based hydrogen storage alloys

In this paper, the Mg_95-X-Ni_x-Y₅ (x = 5, 10, 15) alloy were prepared by vacuum induction melting. The X-ray diffraction was used to analytical phase composition in different states, and the Scanning Electron Microscope and Transmission Electron Microscope were used to characterize the microstructure and crystalline state. Meanwhile, the kinetic properties of isothermal hydrogen adsorption and desorption at different temperatures also were tested by the Sievert isometric volume method. The results indicate that the hydrogenated Mg–Ni–Y samples is a nanocrystalline structure consists of MgH₂, Mg₂NiH₄, and YH₃ phases. And, the in-situ formed YH₃ phase not decompose in the process of dehydrogenation and evenly dispersed in the mother alloy, which plays a paly a positive the catalytic role for the reversible cyclic reaction of Mg and Mg₂Ni phases. In addition, the Ni elements are effectively to improve the thermodynamic properties of the Mg-based hydrogen storage alloy, the desorption enthalpy of the Ni₅, Ni₁₀, and Ni₁₅ samples successively decrease to 84.5, 69.1, and 63.5 kJ/mol H₂. The hydrogen absorption and desorption kinetics of the Mg–Ni–Y alloy are improved obviously with the increase of Ni content, especially for Mg₈₀Ni₁₅Y₅ alloy, which the optimal hydrogenated temperature is reduced to 200 °C, and the 90% of the maximum hydrogen storage capacity can be absorbed within 1 min, about 5.4 wt % H₂. Besides, the dehydrogenated activation energy of the Mg₈₀Ni₁₅Y₅ alloy also is reduced to 67.0 kJ/mol, and it can completely release hydrogen at 320 °C within 5 min, which is almost reached the hydrogen desorption capability of Ni₅ alloy at 360 °C. This means that Ni element is a very positive element to reduce the hydrogen desorption temperature.     

Synthesis and electrochemical properties of binary MgTi and ternary MgTiX (X = Ni,Si) hydrogen storage alloys

Mg-based hydrogen storage alloys are promising candidates for many hydrogen storage applications because of the high gravimetric hydrogen storage capacity and favourable (de)hydrogenation kinetics. In the present study we have investigated the synthesis and electrochemical hydrogen storage properties of metastable binary Mg_yTi_1?y (y = 0.80–0.60) and ternary Mg_0.63Ti_0.27X_0.10 (X = Ni and Si) alloys. The preparation of crystalline, single-phase, materials has been accomplished by means of mechanical alloying under controlled atmospheric conditions. Electrodes made of ball-milled Mg_0.80Ti_0.20 powders show a reduced hydrogen storage capacity in comparison to thin films with the same composition. Interestingly, for a Ti content lower than 30 at.% the reversible storage capacity increases with increasing Ti content to reach a maximum at Mg_0.70Ti_0.30. The charge transfer coefficients (α) and the rate constants (K₁ and K₂) of the electrochemical (de)hydrogenation reaction have been obtained, using a theoretical model relating the equilibrium hydrogen pressure, electrochemically determined by Galvanostatic Intermittent Titration Technique (GITT), and the exchange current. The simulation results reveal improved values for Mg_0.65Ti_0.35 compared to those of Mg_0.80Ti_0.20. The addition of Ni even more positively affects the hydrogenation kinetics as is evident from the increase in exchange current and, consequently, the significant overpotential decrease.     

Phase and morphology evolution study of ball milled Mg–Co hydrogen storage alloys

Ball milled Mg–Co alloys with body-centered cubic structure (BCC) may absorb hydrogen at 258 K with a hydrogen capacity around 3 mass%. The phase and morphology evolution process of Mg₅₀Co₅₀ alloys ball milled for 0.5 h–400 h was studied by X-ray diffraction and scanning electron microscope. The formation mechanism of the Mg₅₀Co₅₀ alloys was clarified. Mg₅₀Co₅₀ alloys ball milled for various durations were found to present different hydrogen storage properties which could result from the phase and morphology difference in these samples.     

An investigation on electrochemical and gaseous hydrogen storage performances of as-cast La1−xPrxMgNi3.6Co0.4 (x = 0–0.4) alloys

The as-cast RE–Mg–Ni-based AB₂-type La_1−xPr_xMgNi_3.6Co_0.4 (x = 0–0.4) alloys were prepared by vacuum induction furnace with a high purity helium gas as the protective atmosphere. The phase composition and microstructure of the as-cast alloys were characterized by XRD, SEM equipped with EDS. The results indicate that the as-cast alloys consist of two phases of LaMgNi₄ and LaNi₅. The measurements of the electrochemical properties show that the discharge capacity of the alloys slightly decreases with Pr content rising. As the Pr content grows from 0 to 0.4, the maximum discharge capacity decreases from 347.0 to 310.4 mAh/g. However, the cycle stability and the high-rate dischargeability of the alloy obviously augment with the Pr content increasing. Furthermore, the measurements of the electrochemical hydrogen storage kinetics reveal that the limiting current density (I_L) first increases then decreases whereas the exchange current density I₀ of the alloys first decreases then increases with the rising amount of Pr substitution, which indicates that the electrochemical dynamic of the alloy electrode are jointly dominated by the charge-transfer resistance and diffusion ability of hydrogen atoms. The measuring of the gaseous hydrogen storage reveals two pressure plateaus appear on each pressure–concentration–isotherm (P–C–T) curve of the as-cast alloys, which correspond to the LaMgNi₄ and LaNi₅ phases. Furthermore, we note that the pressure plateau of the P–C–T curve visibly rises with Pr content increasing.     

Effect of Al content on the structural and electrochemical properties of A2B7 type La–Y–Ni based hydrogen storage alloy

LaY_1.9Ni_10.2−xAl_xMn_0.5 (x = 0–0.6) hydrogen storage alloys have been prepared using a vacuum induction-quenching furnace and annealed at 1148 K for 16 h. The alloys are composed of Ce₂Ni₇- and Gd₂Co₇-type phases and an extra Pr₅Co₁₉-type phase appears when x = 0.6. Aluminum tends to enter the inner AB₅ slabs of Ce₂Ni₇- and Gd₂Co₇-type phases and promotes the generation of new AB₅ slabs. The maximum discharge capacity of the alloy electrodes is stable at approximate 375 mA h/g as x increases from 0 to 0.4 and then decreases to 364.2 mA h/g (x = 0.6). The cycling capacity retention rate at the 300^th cycle is 59.4%, 62.0%, 62.7% and 58.7% for x = 0, 0.2, 0.4 and 0.6, respectively, indicating that the function of aluminum on improving the cyclic stability of the alloy electrodes is limited. The main reason is that the similar pulverization degrees of the alloys are presented during the charge/discharge cycles.     

Enhanced hydrogen storage properties of Ti–Cr–Nb alloys by melt-spin and Mo-doping

Ti–Cr–Nb hydrogen storage alloys with a body centered cubic (BCC) structure have been successfully prepared by melt-spin and Mo-doping. The crystalline structure, solidification microstructural evolution, and hydrogen storage properties of the corresponding alloys were characterized in details. The results showed that the hydrogen storage capacity of Ti–Cr–Nb ingot alloys increased from 2.2 wt% up to around 3.5 wt% under the treatment of melt-spin and Mo-doping. It is ascribed that the single BCC phase of Ti–Cr–Nb alloys was stabilized after melt-spin and Mo-doping, which has a higher theoretical hydrogen storage site than the Laves phase. Furthermore, the melt-spin alloy after Mo doping can further effectively increase the de-/absorption plateau pressure. The hydrogen desorption enthalpy change ΔH of the melt-spin alloy decreased from 48.94 kJ/mol to 43.93 kJ/mol after Mo-doping. The short terms cycling test also manifests that Mo-doping was effective in improving the cycle durability of the Ti–Cr–Nb alloys. And the BCC phase of the Ti–Cr–Nb alloys could form body centered tetragonal (BCT) or face center cubic (FCC) hydride phase after hydrogen absorption and transform to the original BCC phase after desorption process. This study might provide reference for developing reversible metal hydrides with favorable cost and acceptable hydrogen storage characteristics.     

Microstructure and hydrogen storage properties of non-stoichiometric Zr–Ti–V Laves phase alloys

The non-stoichiometric C15 Laves phase alloys namely Zr_0.9Ti_0.1V_x (x = 1.7, 1.8, 1.9, 2.1, 2.2, 2.3) are designed and expected to investigate the role of defect and microstructure on hydrogenation kinetics of AB₂ type Zr-based alloys. The alloys are prepared by non-consumable arc melting in argon atmosphere and annealed at 1273 K for 168 h to ensure the homogeneity. The microstructure and phase constitute of these alloys are examined by SEM, TEM and XRD. The results indicate the homogenizing can reduce the minor phases α-Zr and abundant V solid solution originating from the non-equilibrium solidification of as-cast alloys. Twin defects with {111}<011 > orientation relationship are observed, and the role of defects on hydrogenation kinetics is discussed. Hydrogen absorption PCT characteristics and hydrogenation kinetics of Zr_0.9Ti_0.1V_x at 673–823 K are investigated by the pressure reduction method using a Sievert apparatus. The results show the hypo-stoichiometric alloys preserve faster hydrogenation kinetics than the hyper-stoichiometric ones due to the decrease of dendritic V. The excess content of Zr₃V₃O phase decreases the hydrogenation kinetics and the stability of hydrides. In addition, the different rate controlled mechanisms during hydrogen absorption are analyzed. The effects of non-stoichiometry on the crystal structure and hydrogen storage properties of Zr_0.9Ti_0.1V_x Laves alloys are discussed.     

Phase structures and electrochemical properties of the Laves phase hydrogen storage alloys Zr1−xTix(Ni0.6Mn0.3V0.1Cr0.05)2

The effects of the partial substitution of Ti for Zr in Zr_1−xTi_x(Ni_0.6Mn_0.3V_0.1Cr_0.05)₂ alloys are reported in this paper. The main phases C15 and C14 Laves phases, and secondary phase Zr₇Ni₁₀ were found. With increasing Ti content, abundance of C15 phase decreases and that of C14 phase increases. Increase of Ti content leads to decrease of the lattice parameters of both C15 and C14 phases. Pressure-composition isotherms show a decrease of the stability of the alloy hydride. Ti substitution for Zr in the alloys is effective to improve the activation and high-rate dischargeability. A critical substitution content of Ti is found at x=0.2. The cycling stability and the high rate dischargeability are deteriorated for the alloy electrodes with high Ti content (x>0.3).     

Superior electrochemical hydrogen storage properties of binary Mg–Y thin films

Mg–Y thin films capped with Pd have been prepared by direct current magnetron co-sputtering system. It is found that Mg alloyed with Y in film state forms ultrafine nanocrystalline intermetallic compounds. The structure together with the catalytic effect of Y gives rise to a high electrochemical hydrogen storage capacities and superior activation properties. It is worthy to note that Mg₇₈Y₂₂ film achieves a high discharge capacity of 1590 mAh g⁻¹ without requiring activation process. Moreover, Mg alloyed with Y effectively improves the cyclic stability of Mg-based films ascribing to the anti-corrosion role of Y. For Mg₃₇Y₆₃ film, more than 92％ of the maximum discharge capacity can be maintained after 100 charge–discharge cycles.