Local and crystal structure of Mg1.9Al0.1Ni hydrogen storage alloys during hydrogen absorption–desorption cycling

The evolution of crystal structure and chemical state of Mg_1.9Al_0.1Ni alloy during hydrogen absorption–desorption cycling was examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). We research the hydrogen storage capacity of the Mg_1.9Al_0.1Ni by the H/D kinetic curves. The H/D kinetic curves indicate that the hydrogen storage capacity increased with the increased cycles and the samples were activated after 10 cycles have the maximum hydrogen storage capacity. The local structure of Ni atoms was studied by extended X-ray absorption fine structure (EXAFS). The EXAFS results indicate the Ni–Ni bonds distance has no obviously change with the cycles increasing, whereas the Ni–Mg bond lengths increase, and the Ni–Mg bond lengths are longer obviously than before 10 cycles whereas it has no obviously change after 10 cycles.     

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.     

Ameliorated microstructure and hydrogen absorption/desorption properties of novel Mg–Ni–La alloy doped with MWCNTs and Co nanoparticles

Based on the positive influence of carbon materials and transition metals, a new type of Mg-based composites with particle size of ～800 nm has been designed by doping hydrogenated Mg–Ni–La alloy with multi-walled carbon nanotubes (MWCNTs) and/or Co nanoparticles. The microstructures, temperature related hydrogen absorption/desorption kinetics and dehydrogenation mechanisms are investigated in detail. The results demonstrate that MWCNTs and Co dispersedly distribute on the surface of Mg–Ni–La particles after high-energy ball milling due to powders’ repeated cold welding and tearing. The experimental samples exhibit improved hydrogen storage behaviors and the addition of MWCNTs and Co can further accelerate the de-/hydriding kinetics. For instance, the Mg–Ni–La–Co sample can absorb 3.63 wt% H₂ within 40 min at 343 K. Dehydrogenation analyses demonstrate that the positive effect of MWCNTs is more obvious than that of Co nanoparticles for the experimental samples. The addition of MWCNTs and Co leads to the average dehydrogenation activation energy of experimental samples decreasing to 82.1 and 84.5 kJ mol^?1, respectively, indicating a significant decrease of dehydrogenation energy barriers. In addition, analyses of dehydrogenation mechanisms indicate that the rate-limiting steps vary with the addition of MWCTNs and Co nanoparticles.     

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.     

Crystal structure and cyclic properties of hydrogen absorption–desorption in Pr2MgNi9

We investigated the crystal structure and cyclic hydrogen absorption–desorption properties of Pr₂MgNi₉. The structural model is based on the PuNi₃-type structure; the Mg atom is assumed to substitute for the Pr site in an MgZn₂-type cell. The refined lattice parameters were determined from X-ray diffraction. A wide plateau region was observed in the P–C (pressure composition) isotherm at 298 K. The maximum hydrogen capacity reached 1.12 H/M (1.62 mass%) under a hydrogen pressure of 2.0 MPa. After 1000 hydrogen absorption–desorption cycles, the hydrogen capacity was superior to that of LaNi₅ (82%). Anisotropic lattice strain occurred in the hydriding process. The anisotropic peak-broadening vector was determined to be <001>. The calculated anisotropic lattice strains of the initial cycle and after 1000 cycles were far smaller than those of LaNi₅.     

Crystal structure of GdNi3 with superlattice alloy and its hydrogen absorption–desorption property

We synthesized the intermetallic compound GdNi₃, which has a PuNi₃-type structure (space group R-3m), and investigated its P–C isotherm. The refined lattice parameters were a = 0.4993(1) nm and c = 2.4536(4) nm. In the first absorption process, two plateaus were observed, and the maximum hydrogen capacity reached 1.07 H/M. In the first desorption process, a narrow and sloping plateau was observed at approximately 0.02 MPa. After the first full desorption, 0.6 H/M of hydrogen remained in the sample. This sample showed severe peak broadening in the XRD pattern, indicating that the metal sublattice deformed from the original alloy. No plateau region was observed in the second absorption–desorption cycle.     

Efficient catalytic properties of SO42−/MxOy (M = Cu,Co, Fe) catalysts for hydrogen generation by methanolysis of sodium borohydride

The SO₄^2?/M_xO_y (M = Cu, Co, Fe) catalysts were prepared and applied to hydrogen production from methanolysis of sodium borohydride for the first time. The morphologies and properties of the as-prepared catalysts were characterized by XRD, BET, FT-IR, TEM and SEM-EDX techniques. Under our experimental conditions, SO₄^2?/CuO exhibits much higher catalytic activity than those of SO₄^2?/CoO and SO₄^2?/Fe₂O₃ catalysts and follows the order of SO₄^2?/CuO > SO₄^2?/CoO > SO₄^2?/Fe₂O₃, which is opposite to order of BET surface area, implying that the methanolysis of sodium borohydride is not a structure-sensitive reaction. It can be inferred that both acidic and metallic sites are responsible for the high catalytic performance of the SO₄^2?/M_xO_y catalysts towards NaBH₄ methanolysis. In addition, the effects of the concentrations of NaBH₄ and methanol, catalyst dosage, and reaction temperature on the hydrogen generation rate have been investigated using SO₄^2?/CuO as catalyst. The SO₄^2?/CuO-catalyzed methanolysis reaction follows a power law, i.e. r = A·exp (?13135/RT)·[NaBH₄]^1.01·[CH₃OH]^1.60·[Catalyst]^0.52. The apparent activation energy was calculated to be 13.13 kJ/mol.     

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.     

Evaluation of hydrogen permeation properties of Ni–Ba(Zr0.7Pr0.1Y0.2)O3−δ cermet membranes

In order to obtain chemically stable hydrogen-permeable cermet membranes against CO₂ and H₂O, the composite membranes consisting of Ni and Ba(Zr_0.7Pr_0.1Y_0.2)O_3−δ (BZPY) are fabricated by the dry-press technique and reducing atmosphere sintering process. SEM results show that the cermet membrane is extremely dense and metal nickel is randomly distributed in BZPY oxide matrix. Hydrogen permeation properties of the Ni-BZPY membranes are systemically studied including the influence of the operating temperature, H₂ concentration in feed stream, humidification degree and membrane thickness. The Ni-BZPY membrane presents good chemical stability in humid condition or CO₂-containing environments and is potential candidates for hydrogen separation.     

Studies on the thermal characteristics of hydrides of Mg,Mg2Ni,Mg2Cu and Mg2Ni1−xMx (M = Fe,Co, Cu or Zn; 0 < × < 1) alloys

X-ray results on the alloys of the composition Mg₂Ni_1−xM_x (M = Fe, Co, Cu or Zn; 0 < × < 1) suggest a Mg₂Ni-type structure. The alloys, Mg₂Ni_0.75M_0.25(M = Fe, Co, Cu or Zn) upon hydriding lead to the formation of quarternary hydrides while on dehydriding yield the starting ternary alloys except for copper containing alloys which show multi-phase regions and follow a different path way for the hydriding-dehydriding process. Thermal studies (TG-DTA) on the hydrides indicate the amount of hydrogen evolved as well as the desorption temperatures. The thermodynamic quantities, namely the enthalpies and entropies of formation of the hydrides were deduced from the DTA peak maximum temperature data. The kinetic parameters such as activation energies, reaction rates and orders of the reaction for the decomposition of the hydrides formed from Mg, Mg₂Ni and Mg₂Cu alloys were evaluated from the DTA data. As to the modified Mg₂Ni system, the copper substituted alloys show lower thermal stability and also presents some interesting properties. Hence, it is considered as one of the promising ternary combinations (Mg-Ni-Cu) for hydrogen storage purposes.     

Microstructure and hydrogen storage properties of Zr0.8Ti0.2Co1−xFex (x=0, 0.1, 0.2, 0.3) alloys

In the present study, Zr_0.8Ti_0.2Co_1?xFe_x (x = 0, 0.1, 0.2 and 0.3) alloys were prepared by arc melting method. The effect of Fe substitution on microstructure and hydrogen storage properties was studied systematically. The phase structure and hydrogen storage properties were characterized by X-ray diffraction (XRD), Electron Probe Micro-analysis (EMPA) and Sievert's type volumetric apparatus. XRD and EPMA analysis show that Zr_0.8Ti_0.2Co alloy forms cubic phase ZrCo and traces of ZrCo₂, while the alloys of composition with x = 0.1, 0.2 and 0.3 form cubic phase ZrCo with the secondary Laves phases Zr(Co,Fe)₂ and Zr₂Co. The cell volumes and content of the secondary phase increase gradually as the content of Fe substitution increases. The hydrogen storage experiment shows that Fe substitution for Co ameliorates initial hydriding kinetic property and shortens the incubation duration of the Zr_0.8Ti_0.2Co_1?xFe_x (x = 0.1, 0.2 and 0.3) alloys, compared with Zr_0.8Ti_0.2Co alloy. The improved kinetic property is due to the catalyst effect of the secondary phase, which makes it favorable for the application in International Thermonuclear Experimental Reactor (ITER).     

Mutual effect of extrinsic defects and electronic carbon traps of M-TiO2 (M = V,Co, Ni) nanorod arrays on photoexcited charge extraction of CdS for superior photoelectrochemical activity of hydrogen production

Understanding the photoexcited charge carrier dynamics such as separation, transportation and extraction in smart hybrid nanocomposites is the key to high performance solar cells. Nanocomposites possess advantage of broader solar absorption with their fast photoexcited charge separation and transportation but their use as photocorrosion-stable material is yet to be explored. Also, bulk and surface defects in individual components of the nanocomposites boost the efficiency of the solar cells, despite of the fact the recombination of the photoexcited charges at the interfaces lead to a substantial loss of charges and realizing a big challenge. Herein, the extrinsic defects like bulk and surface defects are induced by transition metal (M = V, Co, Ni) doping of M ? TiO₂ nanorod arrays. Consequently, the hydrothermal synthesis method offers the tuning of the carbon trapping states depending upon the type of the metal doped in M ? TiO₂ that decelerates the charge carrier dynamics in the M-TiO₂/CdS (M = V, Co, Ni) nanocomposites with the increase in the amount of carbon. Excellent charge extraction is observed in VTiO₂ (4% carbon) from its CdS sensitizer with photocurrent density of 2.06 mA/cm² than NiTiO₂ (14.6% carbon), TiO₂ (18.94% carbon) and CoTiO₂ (39.2% carbon) with photocurrent densities of 1.83, 1.46 and 1.34 mA/cm² at 0 V versus Ag/AgCl under 100 mW/cm² light intensity, respectively. This shows primary dependence of photoexcited charge dynamics upon the density of the carbon trapping states to be least while secondary dependence upon the density of the extrinsic defects in M ? TiO₂ to be maximum. This work creates a paradigm for future studies to have a broader insight of the photocatalyst's overall functioning to boost the efficiencies in solar cells by controlling the amount of electronic carbon traps during the synthesis of a large class of inorganic semiconductor photocatalysts.     

Microstructures and electrochemical characteristics of the La0.75Mg0.25Ni2.5Mx (M=Ni, Co; x=0–1.0) hydrogen storage alloys

In order to investigate the influences of the stoichiometric ratios of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structure and the electrochemical performances of the _AB2.5–3.5${\mathrm{AB}}_{2.5–3.5}$-type electrode alloys, the La–Mg–Ni–Co system _{La0.75Mg0.25Ni2.5Mx}${\mathrm{La}}_{0.75}{\mathrm{Mg}}_{0.25}{\mathrm{Ni}}_{2.5}{\mathrm{M}}_x$ (M=Ni$\mathrm{M}=\mathrm{Ni}$, Co; x=0$x=0$, 0.2, 0.4, 0.6, 0.8, 1.0) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The obtained results show that the structures and electrochemical performances of the alloys are closely relevant to the M content. All the alloys exhibit a multiphase structure, including _LaNi2${\mathrm{LaNi}}_2$, (La,Mg)_Ni3$(\mathrm{La},\mathrm{Mg}){\mathrm{Ni}}_3$ and _LaNi5${\mathrm{LaNi}}_5$ phases, and the major phase in the alloys changes from _LaNi2${\mathrm{LaNi}}_2$ to (La,Mg)_Ni3+_LaNi5$(\mathrm{La},\mathrm{Mg}){\mathrm{Ni}}_3+{\mathrm{LaNi}}_5$ with the variety of M content. The electrochemical performances of the alloys, involving the discharge capacity, the high rate discharge (HRD) ability, the activation capability and the discharge potential characteristics, significantly improve with increasing M content. When M content x$x$ increases from 0 to 1.0, the discharge capacity rises from 177.7 to 343.62  mAh/g for the alloy (M=Ni)$(\mathrm{M}=\mathrm{Ni})$, and from 177.7 to 388.7 mAh/g for the alloy (M=Co)$(\mathrm{M}=\mathrm{Co})$. The cycle stability of the alloy first mounts up then declines with growing M content. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed M content (x=1.0)$(x=1.0)$, the substitution of Co for Ni enhances the discharge capacity from 343.62 to 388.7 mAh/g, and the capacity retention ratio (_S100)$(S_{100})$ after 100 charging–discharging cycles from 51.45% to 61.1%.     

Microstructure characteristics,hydrogen storage kinetic and thermodynamic properties of Mg80–xNi20Yx (x = 0–7) alloys

Mg_80–xNi₂₀Y_x (x = 0–7) alloys were successfully prepared by using the vacuum induction melting method. The structural characterizations of the alloys were performed by using X-ray diffraction, scanning electron microscope, transmission electron microscope and X-ray photoelectron spectroscopy measurements. The effects of yttrium content on the microstructure and hydrogen storage properties of the as-cast alloys were investigated. The alloys are composed of a primary phase of Mg₂Ni, lamella eutectic composites of Mg + Mg₂Ni, and some amount of YNi₃. The YNi₃ has completely transformed into in situ formed nanoscale YH₂ and YH₃, with the formation of Mg₂NiH₄. Pulverization of the alloy particles was observed during the hydrogen absorption and desorption cycles. However, the phase composition remains unchanged even after 20 hydrogenation cycles. Yttrium addition significantly improved the hydrogen-absorption kinetic performance of the alloy. In addition, pressure-composition-temperature measurements indicated that the entropy and enthalpy changes for the formation and decomposition of MgH₂ and Mg₂NiH₄ gradually decreased with the increase of yttrium content.     

Phase formation of Ce5Co19-type super-stacking structure and its effect on electrochemical and hydrogen storage properties of La0.60M0.20Mg0.20Ni3.80 (M = La,Pr, Nd,Gd) compounds

In order to investigate the formation mechanism of Ce₅Co₁₉-type super-stacking structure phase, La_0.60M_0.20Mg_0.20Ni_3.80 (M = La, Pr, Nd, Gd) compounds are synthesized by powder sintering method. Rietveld refinements of X-ray diffraction patterns find that La_0.80Mg_0.20Ni_3.80 compound has a single Pr₅Co₁₉-type structure. The Ce₅Co₁₉-type phase appears and increases with the decrease of atomic radius of M, until the La_0.60Gd_0.20Mg_0.20Ni_3.80 compound shows a Ce₅Co₁₉-type single phase structure. The cycling stability and high rate dischargeability (HRD) of the alloy electrodes both improve with the increase of Ce₅Co₁₉-type phase. The capacity retention of La_0.60Gd_0.20Mg_0.20Ni_3.80 compound at the 100th cycle is high to 93.6% and the HRD reaches 66.9% at a discharge current density of 1500 mA g^?1. Moreover after 50 charge/discharge cycles, the Ce₅Co₁₉-type particle retains an intact crystal structure while severe amorphization occurs to Pr₅Co₁₉-type particle as shown in graphical abstract. The cohesive energy obtained from the First-principle calculations is analyzed combined with the experimental results. It is found that the La_0.60Gd_0.20Mg_0.20Ni_3.80 compound with Ce₅Co₁₉-type single phase structure has the highest cohesive energy indicating a more stable structure. This work provides new insights into the superior composition-structure design of LaMgNi system hydrogen storage alloys that may improve the cycling stability.     

Hydrogen storage properties of core-shell structured Mg@TM (TM = Co,V) composites

Target improving the hydrogen sorption properties of Mg, core-shell structured Mg@TM (TM = Co, V) composites were synthesized via an approach combining arc plasma method and electroless plating. The core-shell structures with the MgH₂ core and V or Co containing hydride shells for hydrogenated Mg@TM particles were observed through HAADF-STEM and HRTEM techniques. The measured hydrogenation enthalpy (ΔH_abs = ?70.02 kJ/mol H₂) and activation energy (E_a = 67.66 kJ/mol H₂) of the ternary Mg@Co@V composite were lower than those of binary composites and the pure Mg powder. In addition, the onset dehydrogenation temperature for the hydrogenated ternary composite measured from DSC was 323 °C, about 60 °C lower than that of pure MgH₂. On one hand, these improved properties can be attributed to the core-shell structure which may introduce more contacts between catalysts and Mg, thus providing more nucleation sites for hydrogen sorption. On the other hand, the co-effect of MgCo hydrides (Mg₂CoH₅&Mg₃CoH₅) acting as “hydrogen pump” and V₂H accelerating the dissociation of H₂ might also contribute to the improved hydrogen sorption properties of Mg.     

Effect of transition metal on stability and activity of La-Ca-M-(Al)-O (M = Co,Cr, Fe and Mn) perovskite oxides during partial oxidation of methane

Perovskite oxides of the type of La_xCa_1-xM_yAl_1-yO_3-δ (M = Co, Cr, Fe, Mn; x = 0.5; y = 0.7–1.0) were prepared using the polymerization methods and evaluated via N₂ adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy dispersive X-ray (EDX) spectroscopy, temperature-programmed reduction by hydrogen (TPR-H₂) and temperature-programmed oxidation by oxygen (TPO-O₂). Catalytic behaviour of the perovskite oxides during methane oxidation was studied using a tubular fixed-bed reactor. In a partial oxidation, which proceeded in two steps, there was total oxidation in the first step and CO₂ and H₂O were formed; in the second step, the total oxidation products oxidized methane by (dry and wet) reforming reactions to yield CO and H₂. Total oxidation and the two reforming reactions proceeded on two types of an active centre formed by transition metal ions, oxygen vacancies and oxide ions. The catalytic system La-Ca-Co-Al-O which contained aluminium, decomposed in partial oxidation of methane (POM) into a composite that contained firmly bonded cobalt nanoparticles in the surface of a substrate made up of La₂O₃, CaO and Al₂O₃ which catalysed POM with a high methane conversion and hydrogen selectivity.     

Characterization and activity test of commercial Ni/Al2O3, Cu/ZnO/Al2O3 and prepared Ni–Cu/Al2O3 catalysts for hydrogen production from methane and methanol fuels

In this study, methane and methanol steam reforming reactions over commercial Ni/Al₂O₃, commercial Cu/ZnO/Al₂O₃ and prepared Ni–Cu/Al₂O₃ catalysts were investigated. Methane and methanol steam reforming reactions catalysts were characterized using various techniques. The results of characterization showed that Cu particles increase the active particle size of Ni (19.3 nm) in Ni–Cu/Al₂O₃ catalyst with respect to the commercial Ni/Al₂O₃ (17.9). On the other hand, Ni improves Cu dispersion in the same catalyst (1.74%) in comparison with commercial Cu/ZnO/Al₂O₃ (0.21%). A comprehensive comparison between these two fuels is established in terms of reaction conditions, fuel conversion, H₂ selectivity, CO₂ and CO selectivity. The prepared catalyst showed low selectivity for CO in both fuels and it was more selective to H₂, with H₂ selectivities of 99% in methane and 89% in methanol reforming reactions. A significant objective is to develop catalysts which can operate at lower temperatures and resist deactivation. Methanol steam reforming is carried out at a much lower temperature than methane steam reforming in prepared and commercial catalyst (275–325 °C). However, methane steam reforming can be carried out at a relatively low temperature on Ni–Cu catalyst (600–650 °C) and at higher temperature in commercial methane reforming catalyst (700–800 °C). Commercial Ni/Al₂O₃ catalyst resulted in high coke formation (28.3% loss in mass) compared to prepared Ni–Cu/Al₂O₃ (8.9%) and commercial Cu/ZnO/Al₂O₃ catalysts (3.5%).