Hydrogen adsorption of O/N-rich hierarchical carbon scaffold decorated with Ni nanoparticles: Experimental and computational studies

Hierarchical carbon scaffold (HCS) with multi-porous structures, favoring hydrogen diffusion and physisorption is doped with 2–10 wt % Ni for storing hydrogen at ambient temperature. Due to N- and O-rich structure of melamine-formaldehyde resin used as carbon precursor, homogeneous distribution of heteroatoms (N and O) in HCS is achieved. 2 wt % Ni-doped HCS shows the highest hydrogen capacity up to 2.40 wt % H₂ (T = 298 K and p (H₂) = 100 bar) as well as excellent reversibility of 18.25 g H₂/L and 1.25 wt % H₂ (T = 298 K and p (H₂) = 50 bar) and electrical production from PEMFC stack up to 0.7 Wh upon eight cycles. Computations and experiments confirm strong interactions between Ni and heteroatoms, leading to uniform distribution small particles of Ni. This results in enhancing reactive surface area for hydrogen adsorption and preventing agglomeration of Ni nanoparticles upon cycling. Ni K-edge XANES spectra simulated from the optimized structure of Ni-doped N/O-rich carbon using DFT calculations are consistent with the experimental spectra and suggest electron transfer from Ni to hydrogen to form Ni–H bond upon adsorption. Considering low desorption temperature (323 K), not only chemisorbed hydrogen is involved in adsorption mechanisms but also physisorption and spillover of hydrogen.     

On the long-term cyclic stability of near-eutectic Mg–Mg2Ni alloys

In this investigation, we report the cyclic performance, microstructure and thermal properties of near eutectic Mg–Ni alloys with different Ni contents (4.4, 11.3 and 16.3 at%). The starting cast ingots are mechanically chipped to flakes of about 400 μm, all displaying composite structures characterized by a typical eutectic microstructure with rather coarse features (1–5 μm). The flakes are cycled 1000 times at 330 °C under 30/1 bar H₂ for the absorption/desorption processes. The hydrogen storage capacity is maintained throughout the cycling: 5.09, 4.46 and 3.49 wt% H₂ for Ni16.3, Ni11.3 and Ni4.4 (at%), respectively. No significant microstructural change is observed, indicating the excellent stability of the alloys at elevated temperatures. Nevertheless, a marked porosity, and spheroidal Mg₂Ni clusters can be noted after cycling, however their exact contribution to reaction kinetics has yet to be fully elucidated. An attempt is made to estimate the dehydrogenation activation energy of Ni16.3, and the calculated value seems comparable to that obtained for an early cycling stage (10 cycles). In the light of the superior stability under cyclic service and the low decomposition temperature, the Mg–Mg₂Ni system is shown to possess an excellent potential for long-term hydrogen and heat storage applications.     

Nanostructured hydrogen storage materials prepared by high-energy reactive ball milling of magnesium and ferrovanadium

Hydrogen storage nanocomposites prepared by high energy reactive ball milling of magnesium and vanadium alloys in hydrogen (HRBM) are characterised by exceptionally fast hydrogenation rates and a significantly decreased hydride decomposition temperature. Replacement of vanadium in these materials with vanadium-rich Ferrovanadium (FeV, V80Fe20) is very cost efficient and is suggested as a durable way towards large scale applications of Mg-based hydrogen storage materials. The current work presents the results of the experimental study of Mg–(FeV) hydrogen storage nanocomposites prepared by HRBM of Mg powder and FeV (0–50 mol.%). The additives of FeV were shown to improve hydrogen sorption performance of Mg including facilitation of the hydrogenation during the HRBM and improvements of the dehydrogenation/re-hydrogenation kinetics. The improvements resemble the behaviour of pure vanadium metal, and the Mg–(FeV) nanocomposites exhibited a good stability of the hydrogen sorption performance during hydrogen absorption – desorption cycling at T = 350 °C caused by a stability of the cycling performance of the nanostructured FeV acting as a catalyst. Further improvement of the cycle stability including the increase of the reversible hydrogen storage capacity and acceleration of H₂ absorption kinetics during the cycling was observed for the composites containing carbon additives (activated carbon, graphite or multi-walled carbon nanotubes; 5 wt%), with the best performance achieved for activated carbon.     

MgH2–TiF4-MWCNTs based hydrogen storage tank with central tube heat exchanger

Improvement of hydrogen sorption kinetics of MgH₂–TiF₄-MWCNTs based tank by addition of central tube heat exchanger and enhancement of hydrogen diffusion is proposed. After doping with TiF₄ and MWCNTs, dehydrogenation temperature of MgH₂ decreases significantly (ΔT = up to 90 °C). Superior hydrogen permeability, favoring hydrogen sorption kinetics is detected at hydrogen supply side to the middle of the tank, while effective heat transfer during exothermic hydrogenation is assured by the temperature increment of heat exchanger fluid (compressed air at room temperature). Hydrogen desorption and absorption can be completed within 120–150 and 25 min, respectively, up to twice as fast as the tank without heat exchanger from the previous studies. Due to fast hydrogenation rate resulting in short reaction time at high equilibrium temperature (up to 390 °C), particle agglomeration and/or sintering of MgH₂ upon cycling are prevented. Enhanced de/rehydrogenation rates and suppression of MgH₂ particle growth during cycling yield to considerable reversibility upon 20 de/rehydrogenation cycles with storage capacity up to 5.60 wt % H₂ (82% theoretical value). By increasing operating temperature to 330–335 °C, hydrogen released with constant flow rate of 0.30 standard L/min is prolonged up to three times, favoring electrical power production of PEMFC stack. Electrical performances obtained from PEMFC stack (13 single cells) supplied with hydrogen gas from MgH₂-based tank are also investigated.     

Hydrogen uptake of manganese oxide-multiwalled carbon nanotube composites

Hydrogen uptake of pristine multi-walled carbon nanotubes is increased more than three-fold at 298 K and hydrogen pressure of 4.0 MPa, upon addition of hydrogen spillover catalyst manganese oxide, from 0.26 to 0.94 wt%. Simple and convenient in situ reduction method is used to prepare Mn-oxide/MWCNTs composite. XRD, FESEM, and TEM demonstrates nanostructural characterization of pristine MWCNTs and composite. TGA analysis of Mn-oxide/MWCNTs composites showed a single monotonous fall related to MWCNTs gasification. Enhancement of hydrogen storage capacity of composite is attributed to spillover mechanism owing to decoration of Mn-oxide nanoparticles on outer surface of MWCNTs. Hydrogen uptake follows monotonous dependence on hydrogen pressure. Oxide-MWCNTs composite not only shows high hydrogen storage capacity as compared to pristine, but also exhibit significant cyclic stability upon successive adsorption–desorption cycles.     

Effect of Cr substitution by Ni on the cycling stability of Mg2Ni alloy using EXAFS

This paper describes the hydrogen storage properties of Mg₂Ni_0.9Cr_0.1 alloy and aims to elucidate the effect of doping Cr on the hydrogen sorption/desorption kinetics upon cycling. Mg₂Ni_0.9Cr_0.1 alloy shows stable absorption capacity, and its absorption/desorption rates further improve after cycling. The calculated activation energy for dehydrogenation was 53 kJ/mol at the 3rd cycle, and decreased to 36 kJ/mol at the 20th cycle. XRD combined with SEM exhibits that Cr dopant substitutes for Mg or Ni after ball milling and the lattice structure remains stable over 20 cycles. EXAFS was used to investigate the local coordination of Ni and Cr atoms in the ball-milled and cycled samples. For the ball-milled sample, the strong Cr–Ni bonds weaken the Cr–Mg bonds, thereby destabilizing all Cr-doped phases. After 20 cycles, the stable Ni₁–Mg₁ bonds may be dominant and control the structural stability of Mg₂Ni phases.     

Revealing the interfacial phenomenon of metal-hydride formation and spillover effect on C48H16 sheet by platinum metal catalyst (Pt (n=1-4)) for hydrogen storage enhancement

Hydrogen is a worldwide green energy carrier, however due its low storage capacity, it has yet to be widely used as an energy carrier. Therefore, the quantum chemical method is being employed in this investigation for better understand the hydrogen storage behaviour on Pt _(n = 1-4) cluster decorated C₄₈H₁₆ sheet. The Pt_(n = 1-4) clusters are strongly bonded on the surface of C₄₈H₁₆ sheet with binding energies of ?3.06, ?4.56, ?3.37, and ?4.03 eV respectively, while the charge transfer from Pt_(n = 1-4) to C₄₈H₁₆ leaves an empty orbital in Pt atom, which will be crucial for H₂ adsorption. Initially, the molecular hydrogen is adsorbed on Pt_(n = 1-4) decorated C₄₈H₁₆ sheet through the Kubas interaction with adsorption energies of ?0.85, ?0.66, ?0.72, and ?0.57 eV respectively, while H–H bond is elongated due to the transfer of electron from σ (HH) orbital to unfilled d orbital of the Pt atom, resulting in a Kubas metal-dihydrogen complexes. Furthermore, the dissociative hydrogen atoms adsorbed on Pt_(n = 1-4) decorated C₄₈H₁₆ sheet have adsorption energies of ?1.14 eV, ?1.02 eV, ?0.95 eV, and ?1.08 eV, which are greater than the molecular hydrogen adsorption on Pt_(n = 1-4) cluster supported C₄₈H₁₆ sheet with lower activation energy of 0.007, 0.109, 0.046, and 0.081 eV respectively. To enhance the dissociative hydrogen adsorption energy, positive and negative external electric fields are applied in the charge transfer direction. Increasing the positive electric field makes H–H bond elongation and good adsorption, whereas increasing the negative electric field results H–H bond contraction and poor adsorption. Thus, by applying a sufficient electric field, the H₂ adsorption and desorption processes are can be easily tailored.     

Improved hydrogen gas sensing performance of Pd–Ni alloy thin films

This study examined the palladium (Pd)-nickel (Ni) alloy films' ability to detect hydrogen (H₂) at various Ni concentrations. The co-sputtering method was used to make the Pd–Ni alloy sensors. The response of the Pd–Ni alloys sensor reduced linearly as Ni_8% concentration was added to Pd, and the resistance of the Pd–Ni alloys was reversible upon exposure to H₂ gas with absorption and desorption characteristics. The experimental findings demonstrated that the Pd–Ni alloy sensor response time of 11 s was much faster than that of pure Pd, with great selectivity and stability for a period of 90 days.     

Improved hydrogen production performance of Ni–Al2O3/CaO–CaZrO3 composite catalyst for CO2 sorption enhanced CH4/H2O reforming

Bifunctional composite catalysts are very intrigued to produce hydrogen via CO₂ sorption enhanced CH₄/H₂O reforming. However, their hydrogen production performance declined over multiple cycles, owing to the structure collapse and the sintering of active component under high-temperature regeneration. This work reported the facile synthesis of long-lasting Ni–Al₂O₃/CaO–CaZrO₃ composite catalysts with less inert components (36 wt%) for stable hydrogen production over the multiple cycles of CO₂ sorption enhanced CH₄/H₂O reforming. The effects of reaction and regeneration temperature on the hydrogen production performance of Ni–Al₂O₃/CaO–CaZrO₃ were explored. Ni–Al₂O₃/CaO–CaZrO₃ demonstrated high activity and stability while fixing reaction temperature as 600 °C and regeneration temperature as 750 °C. Of particular importance, H₂ concentration was 98 vol% even after 10 hydrogen production cycles due to the inert component CaZrO₃ having a cross-linked structure. The distribution of CaZrO₃ in the composite as a coral-like structure inhibited the sintering of CaO through high Taman temperature and physical separation. Moreover, it provided the skeleton support and pore volume for the repeated expansion and contraction process of CaO to CaCO₃ during the cycling process. Finally, the sintering of Ni slowed down in appropriate regeneration temperature to maintain the structure of the composite catalyst, which further improved the catalyst's stability over multiple cycles.     

Effect of Ti-based nanosized additives on the hydrogen storage properties of MgH2

MgH₂-based nanocomposites were synthesized by high-energy reactive ball milling (RBM) of Mg powder with 0.5–5 mol% of various catalytic additives (nano-Ti, nano-TiO₂, and Ti₄Fe₂O_x suboxide powders) in hydrogen. The additives were shown to facilitate hydrogenation of magnesium during RBM and substantially improve its hydrogen absorption-desorption kinetics. X-ray diffraction analysis showed the formation of nanocrystalline MgH₂ and hydrogenation of nano-Ti and Ti₄Fe₂O_x. The possible reduction of TiO₂ during RBM in hydrogen was not observed, which is in agreement with lower hydrogenation capacity of the corresponding composite, 5.7 wt% for Mg + 5 mol% nano-TiO₂ compared to 6.5 wt% for Mg + 5 mol% nano-Ti. Hydrogen desorption from the as-prepared composites was studied by Thermal Desorption Spectroscopy (TDS) in vacuum. A significant lowering of the hydrogen desorption temperature of MgH₂ by 30–90 °C in the presence of the additives is associated with lowering activation energy from 146 kJ/mol for nanosized MgH₂ down to 74 and 67 kJ/mol for MgH₂ modified with nano-TiO₂ and Ti₄Fe₂O_0.3 additives, respectively. After hydrogen desorption at 300–350 °C, these materials are able to absorb hydrogen even at room temperature. It is shown that nano-structuring and addition of Ti-based catalysts do not decrease thermodynamic stability of MgH₂. The thermodynamic parameters, obtained from hydrogen desorption isotherms for the Mg–Ti₄Fe₂O_0.3 nanocomposite, ΔH_des = 76 kJ/mol H₂ and ΔS_des = 138 J/K·mol H₂, correspond to the reported literature values for pure polycrystalline MgH₂. Hydrogen absorption-desorption characteristics of the composites with nano-Ti remain stable during at least 25 cycles, while a gradual decay of the reversible hydrogen capacity occurred in the case of TiO₂ and Ti₄Fe₂O_x additives. Cycling stability of Mg/Ti₄Fe₂O_x was substantially improved by introduction of 3 wt% graphite into the composite.     

Fundamentals of hydrogen storage processes over Ru/SiO2 and Ru/Vulcan

Hydrogen adsorption and desorption over Ru/SiO₂ and Ru/Vulcan are investigated in terms of hydrogen storage and release characteristics by both dynamic and static experiments. Ru particle dispersions as a function of metal loading were determined by HR-TEM and volumetric chemisorption experiments. Vulcan was more accommodating for spillover hydrogen than SiO₂. High Ru dispersions, i.e., small particle sizes, favored the amount of hydrogen spillover to Vulcan, as revealed by temperature programmed desorption (TPD) of hydrogen. TPD of hydrogen under He flow experiments over Ru/SiO₂ and Ru/Vulcan materials revealed a low temperature process (up to 200 °C) attributed to desorption of weakly bound hydrogen from Ru metal surface. A high temperature process (above 450 °C) was attributed to diffusion of hydrogen from the support to the Ru particle and desorption at the Ru sites. Hydrogen adsorbs strongly on Ru metal, as indicated by the initial heats of H₂ adsorption measured as 100 kJ/mol over 1 wt% Ru/Vulcan by adsorption calorimetry. At higher coverages, heat of adsorption of hydrogen was measured as 10 kJ/mol. Low heat of adsorption of hydrogen at high coverages indicate multilayer weak adsorption of hydrogen over the storage material, which can desorb at lower temperatures.     

Highly efficient sputtered Ni-doped Cu2O photoelectrodes for solar hydrogen generation from water-splitting

Hydrogen gas can be converted to electricity through fuel cells and is considered as a friendly energy source. Herein, pure Cu₂O and Ni-doped Cu₂O thin films were deposited on glass substrates using the RF/DC-sputtering technique for hydrogen production via the photoelectrochemical (PEC) water-splitting process. The preferred orientation for pure and Ni-doped Cu₂O films was (111) crystallographic plane. The average nanograins size was decreased from 32.17 nm for pure to 10.40 nm through the doping process with Ni content. Field-emission scanning electron microscopy (FE-SEM) and ImageJ analysis showed that the pure Cu₂O and Ni-doped Cu₂O were composed of normal distribution of nanograins in a regular form. The optical bandgap of the Cu₂O film was decreased from 2.35 eV to 1.9 eV after doping with 2.6 wt% of Ni-dopants. The photoluminescence (PL) spectra for all the sputtered films were recorded at room temperature to examine the effect of Ni-dopants in the Cu₂O lattice. Pure and Ni-doped Cu₂O films were applied for PEC water splitting for hydrogen (H₂) production under white light and monochromatic illumination. The PEC studies displayed that increasing the Ni content up to 2.6 wt% in the pure Cu₂O films led to an increase in the photocurrent density to reach ?5.72 mA/cm². The optimum photoelectrode was studied for reproducibility, stability, and electrochemical impedance. The incident photon to current conversion efficiency (IPCE%) was 16.35% at 490 nm, and the applied bias photon to current conversion efficiency (ABPE%) was 0.90% at 0.65 V. Consequently, Ni-doped Cu₂O photoelectrodes are efficient and low-cost for practical and industrial solar H₂ production.     

Enhanced hydrogen-storage properties of MgH2 by Fe–Ni catalyst modified three-dimensional graphene

High dehydrogenation temperature and slow dehydrogenation kinetics impede the practical application of magnesium hydride (MgH₂) serving as a potential hydrogen storage medium. In this paper, Fe–Ni catalyst modified three-dimensional graphene was added to MgH₂ by ball milling to optimize the hydrogen storage performance, the impacts and mechanisms of which are systematically investigated based on the thermodynamic and kinetic analysis. The MgH₂+10 wt%Fe–Ni@3DG composite system can absorb 6.35 wt% within 100 s (300 °C, 50 atm H₂ pressure) and release 5.13 wt% within 500 s (300 °C, 0.5 atm H₂ pressure). In addition, it can absorb 6.5 wt% and release 5.7 wt% within 10 min during 7 cycles, exhibiting excellent cycle stability without degradation. The absorption-desorption mechanism of MgH₂ can be changed by the synergistic effects of the two catalyst materials, which significantly promotes the improvement of kinetic performance of dehydrogenation process and reduces the hydrogen desorption temperature.     

Atom doping in α-Fe2O3 thin films to prevent hydrogen permeation

Prevention of hydrogen (H) penetration into passive films and steels plays a vital role in lowering hydrogen damage. This work reports effects of atom (Al, Cr, or Ni) doping on hydrogen adsorption on the α-Fe₂O₃ (001) thin films and permeation into the films based on density functional theory. We found that the H₂ molecule prefers to dissociate on the surface of pure α-Fe₂O₃ thin film with adsorption energy of −1.18 eV. Doping Al or Cr atoms in the subsurface of α-Fe₂O₃ (001) films can reduce the adsorption energy by 0.03 eV (Al) or 0.09 eV (Cr) for H surface adsorption. In contrast, Ni doping substantially enhances the H adsorption energy by 1.08 eV. As H permeates into the subsurface of the film, H occupies the octahedral interstitial site and forms chemical bond with an O atom. Comparing with H subsurface absorption in the pure film, the absorption energy decreases by 0.01–0.22 eV for the Al- and Cr-doped films, whereas increases by 0.82–0.96 eV for the Ni-doped film. These results suggest that doping Al or Cr prevents H adsorption on the surface or permeation into the passive film, which effectively reduces the possibility of hydrogen embrittlement of the underlying steel.     

Cycling and engineering properties of highly compacted sodium alanate pellets

Sodium alanate powder comprised of NaH and Al was doped with 3 mol% titanium chloride (TiCl₃) and pelletized into highly compacted cylindrical pellets. The pelletization process was performed to improve thermal conductivity and volumetric hydrogen capacity of the metal hydride, compared to loose or tapped powder, which are vital requirements for on-board hydrogen storage applications. The pelletization process was performed over a range of 69–345 MPa (10–50 kPSI) with a 95% increase in density and improvement in thermal conductivity 18 times greater compared to powder at the maximum pelletization pressure (1.60 g/cm³ and 0.82 g/cm³; 9.09 W/m K and 0.50 W/m K, respectively). Hydrogen cycling capacities and kinetics were not adversely affected by the pelletization process although 10 cycles are required to obtain full hydrogen capacity. Pellet cycling capacity maintained a stable 4 wt% H₂ over 50 cycles. Ti-doped NaH + Al pellets exhibited similar thermal cycling expansion as with the loose powder; within 30 cycles there was a 50% loss in pellet density and by 50 cycles the loss in pellet structural integrity made handling problematic.     

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.     

Sustainable and selective hydrogen production by steam reforming of bio-based ethylene glycol: Design and development of Ni–Cu/mixed metal oxides using M (CeO2, La2O3, ZrO2)–MgO mixed oxides

Hydrogen (H₂) production in a clean and green manner via renewable sources is at present of great interest. Ethylene glycol, a bio-based feedstock, offers a sustainable route for high purity H₂ production. In the current investigation, MgO based mixed metal oxides containing CeO₂, La₂O₃ and ZrO₂ were synthesized and used to support 20 wt% Ni–Cu (1:1). The impacts of altering support characteristics on catalytic behavior have been studied and compared in H₂ synthesis via ethylene glycol steam reforming (SR), employing various characterization techniques such as XRD, SEM, EDX, TEM, H₂-TPR, H₂-TPD, TG-DSC and BET. Further, high resolution XPS studies were performed to explore the valence states and effectiveness of surface engineering of the catalysts. Assessment of the efficacy of catalysts was done via several parameters such as reactant conversion, H₂ concentration and long-term stability. All the synthesized materials produced encouraging results with high H₂ yield and conversion under the said operating conditions [T- 623 to 773 K; GHSV - 3120 to 6240 h^?1; P - 0.1 MPa; S/C - 3 to 7.5 mol/mol]. Amongst the three catalysts, Ni–Cu/La₂O₃–MgO and Ni–Cu/CeO₂–MgO exhibited superior behavior for high H₂ production. Ni–Cu/La₂O₃–MgO was better in comparison to Ni–Cu/CeO₂–MgO in terms of reactant conversion whereas Ni–Cu/CeO₂–MgO showed highest H₂ concentration (98 mol %) and improved stability along with absence of carbon deposition owing to its high mobile oxygen vacancies in its lattice. The highly active cubic CeO₂ species and its long-term durability (up to 8 cycles) owing to its exceptional redox property further justified its efficacy. The optimized process showed that at T = 773 K, GHSV = 3120 h^?1, S/C = 4.5 mol/mol for Ni–Cu/La₂O₃–MgO and Ni–Cu/CeO₂–MgO and at T = 773 K, GHSV = 3120 h^?1, S/C = 6 mol/mol and for Ni–Cu/ZrO₂–MgO, maximum H₂ concentration was obtained. At the end, reaction pathway followed by the catalysts was proposed.     

Effect of Ni content on the hydrogen storage behavior of ZrCo1−xNix alloys

ZrCo_1−xNi_x (x = 0, 0.1, 0.2 and 0.3) alloys were prepared and their hydrogen storage behavior were studied. ZrCo_1−xNi_x alloys of compositions with x = 0, 0.1, 0.2 and 0.3 prepared by arc-melting method and characterized by X-ray diffraction analysis. XRD analysis showed that the alloys of composition with x = 0, 0.1, 0.2 and 0.3 forms cubic phase similar to ZrCo with traces of ZrCo₂ phase. A trace amount of an additional phase similar to ZrNi was found for the alloy with composition x = 0.3. Hydrogen desorption pressure–composition–temperature (PCT) measurements were carried out using Sievert's type volumetric apparatus and the hydrogen desorption pressure–composition isotherms (PCIs) were generated for all the alloys in the temperature range of 523–603 K. A single sloping plateau was observed for each isotherm and the plateau pressure was found to increase with increasing Ni content in ZrCo_1−xNi_x alloys at the same experimental temperature. A van't Hoff plot was constructed using plateau pressure data of each pressure–composition isotherm and the thermodynamic parameters were calculated for desorption of hydrogen in the ZrCo_1−xNi_x–H₂ systems. The enthalpy and entropy change for desorption of hydrogen were calculated. In addition, the hydrogen absorption–desorption cyclic life studies were performed on ZrCo_1−xNi_x alloys at 583 K up to 50 cycles. It was observed that with increasing Ni content the durability against disproportionation of alloys increases.     

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.     

Stability of LaNi5-xCox alloys cycled in hydrogen — Part 1 evolution in gaseous hydrogen storage performance

In this study, the evolution trends in various hydrogen storage properties as well as kinetics performance of LaNi_5−xCo_x (x = 0, 0.25, 0.50 and 0.75) alloys up to 1000 cycles are studied, and the effects of Co on the long-term hydrogen absorption/desorption properties are revealed. The alloys have single LaNi₅ phase structure. The cell volume increases with increasing Co content, resulting in a lower hydrogen absorption/desorption plateau pressure and a more stable hydride phase. The alloys have good kinetics performance and can fully absorb hydrogen within 300 s. The hydrogen absorption rate increases with either cycling or Co addition, but neither of them changes the rate limiting step which remains to be diffusion controlled model in the temperature range of 343–383 K. With cycling, an intermediate γ phase emerges with the coexistence of α and β phases indicated by an extra higher plateau in P-C-T curves. This γ phase acts as a buffer releasing the microstrains which is reflected from the slower capacity degradation, and the significant decrease in hysteresis and slope factor upon its appearance. Moreover, the c/a value increases after 1000 cycles which also relieves the microstrains in the alloys. Co addition not only enhances the buffer effect of γ phase by partially combining it with β phase, but also promotes the increasing degree of c/a value, contributing to a better crystal structure, bigger particle size and higher cycle stability during long-term cycling.