Hydrogen Absorption Capacity Research Articles

Ti/Cr regulated and strategic Ce doped V-Ti-Cr-Mn-Fe high-entropy alloys with extraordinary reversible hydrogen storage properties at ambient temperature

High-entropy alloys (HEAs) are garnering widespread interest due to their exceptional hydrogen storage capabilities at ambient temperatures. Herein, a series of HEAs composed of V-Ti-Cr-Mn-Fe with varying Ti/Cr ratios has been synthesized via arc melting to serve as carrier materials for room-temperature hydrogen storage. Thanks to the composition of a large amount of body centered cubic (BCC) phase V32TixCr58-xMn5Fe5 exhibits excellent hydrogen storage performance, and the hydrogen absorption capacity of these HEAs escalates while the desorption capacity initially rises followed by a decline with an increase in the Ti/Cr ratio. Notably, the HEA with a Ti/Cr ratio of 1.0, namely V32Ti29Cr29Mn5Fe5, demonstrates exceptional performance by absorbing 3.55 wt% H2 within 60 min and rapidly releasing 2.16 wt% H2 within 5 min at 303 K. Further enhancement is achieved with the strategic doping of Ce in the V32Ti29Cr29Mn5Fe5, which leads to the removal of the Ti-rich phase and the incorporation of CeO2, significantly improves the activation performance, allowing the Ce-doped HEA to reach saturation in the 3rd hydrogen absorption cycle. Consequently, the hydrogen ab-/desorption capacities at ambient temperature are further augmented to 3.73 wt% and 2.26 wt%, respectively, and the enthalpies of hydrogen ab-/desorption are significantly reduced to −25.0 and 23.4 kJ/mol H2, marking a new benchmark for V-based HEAs. Dramatically, DFT calculations suggestes that the incorporation of Ce diminishes the structure energy of BCC phase structure for V32Ti29Cr29Mn5Fe4Ce1 as well as elongates the average distance of M−H from 1.955 Å to 1.969 Å, which corroborate the experimental results, offering profound insights into the underlying mechanisms of hydrogen storage within BCC-phase HEAs at ambient temperature.

FeNi3 alloy doped carbon spheres for improving hydrogen storage performance of MgH2

MgH2 is one of the ideal hydrogen storage materials because of its high hydrogen storage density, but the thermodynamic stability and slow kinetics of Mg/MgH2 system hinder its practical application. Transition metal catalyst doping has become an important strategy to improve the hydrogen storage kinetics of MgH2. In this work, FeNi3@CS was prepared by solvothermal method with carbon spheres (CS) as the support, and introduced into Mg/MgH2 system to prepare MgH2–FeNi3@CS composite. The initial dehydrogenation temperature of MgH2–FeNi3@CS composite is 565 K, which is 100 K lower than additive-free MgH2. At 423 K, MgH2–FeNi3@CS composite could absorb 4.5 wt% H2, while the hydrogen absorption capacity of MgH2 without additives is only 2.0 wt%. After 10 cycles, the hydrogenation and dehydrogenation capacity could be maintained at 5.6 wt% and 4.5 wt%, respectively. In addition, the activation energy of MgH2–FeNi3@CS composite decreased by 52 kJ/mol compared with MgH2. FeNi3 was in situ converted to Mg2NiH4 and Fe after hydrogenation-ball milling, which were considered as the catalytic active substances in Mg/MgH2 system. The synergistic catalysis of Mg2Ni/Mg2NiH4, Fe and carbon materials has a positive effect on improving the hydrogen storage performance of Mg/MgH2 system.

Enhancing hydrogen storage properties of MgH2 via reaction-induced construction of Ti/Co/Mn-based multiphase catalytic system

The inherent kinetic limitations and high operating temperatures of magnesium hydride (MgH2) hinder its practical applications. Herein, we report the successful synthesis of a TiO2@MnCo2O4.5 composite transition metal oxide catalyst and investigate its effect on the hydrogen storage performance of MgH2. TiO2@MnCo2O4.5 exhibits exceptional catalytic activity in the hydrogen dissociation and recombination reactions of during absorption and desorption processes, reducing the dehydrogenation activation energy of MgH2 to 75.54 kJ/mol. Notably, the MgH2-6 wt% TiO2@MnCo2O4.5 system releases 6.04 wt% H2 within 30 min at 250 °C, and 4.98 wt% H2 within 120 min at 225 °C. Furthermore, it can absorb 5.08 wt% H2 within 3 min at 150 °C and achieve a hydrogen absorption capacity of 2.02 wt% within 30 min even at 30 °C. The reaction-induced decomposition and phase transformation of TiO2@MnCo2O4.5 create a multiphase, multi-site catalytic environment. The hydrogen storage system based on the coexistence of Mg6MnO8, Mn, Ti2O3, and CoO features abundant diffusion pathways and nucleation sites, playing a critical role in suppressing the energy barriers for MgH2 hydrogen absorption and desorption reactions. These findings provide a meaningful theoretical foundation for the microstructural optimization and performance regulation of Mg-based hydrogen storage materials.

Investigating the Effects of Transition Metals and Activated Carbon on Hydrogenation Characteristics of Severely Deformed ZK60 Processed by High-Energy Ball Milling.

The synergic effects of activated carbon and transition metals on the hydrogenation characteristics of commercial ZK60 magnesium alloy were investigated. Severe plastic deformation was performed using equal-channel angular pressing with an internal die angle of 120° and preheating at 300 °C. The ZK60 alloy samples were processed for 12 passes using route BA. The deformed ZK60 alloy powder was blended with activated carbon and different concentrations of transition metals (Ag, Pd, Co, Ti, V, Ti) using high-energy ball milling for 20 h at a speed of 1725 rpm. The amount of hydrogen absorbed and its kinetics were calculated using Sievert's apparatus at the higher number of cycles at a 300 °C ab/desorption temperature. The microstructure of the powder was analyzed using an X-ray diffractometer and scanning electron microscope. The results indicated that 5 wt% activated carbon presented the maximum hydrogen absorption capacity of 6.2 wt%. The optimal hydrogen absorption capacities were 7.1 wt%, 6.8 wt%, 6.7 wt%, 6.64 wt%, 6.65 wt%, and 7.06 wt% for 0.5 Ag, 0.3 Co, 0.1 Al, 0.5 Pd, 2 Ti, and 0.5 V, respectively. The hydrogen absorption capacities were reduced by 35.21%, 26.47%, 41.79%, 21.68%, 26.31%, and 26.34% after 100 cycles for 5C0.5Ag, 5C0.3Co, 5C0.1Al, 5C0.5Pd, 2Ti, and 5C0.5V, respectively. Hydrogen absorption kinetics were significantly improved so that more than 90% of hydrogen was absorbed within five minutes.

Size-dependent activity modulation of supported Ni nanocatalysts for efficient solid-state hydrogen storage in magnesium

The activity of Nickel (Ni)-based catalysts strongly depends on their particle size and dispersion; however, achieving controllable preparation of uniform particle size with high activity remains a great challenge for Ni-based catalysts to promote efficient hydrogen storage. Here, we employ a facile Carbothermal Shock (CTS) method to obtain carbon fiber-loaded Ni-based nanocatalysts (Ni@CC) with high dispersibility and size-dependent properties, which can exhibit superior catalytic effects for solid-state hydrogen storage in MgH2. It was found that the shorter the CTS duration, the smaller the size of the Ni nanoparticles, and the better the catalytic effect. Among these, the MgH2-Ni@CC with a CTS duration of 30 s showed the best hydrogen storage performance. Its activation energy for hydrogen release was significantly decreased from 158.3 kJ⋅mol−1 for milled MgH2 to 98.6 kJ⋅mol−1. More importantly, the retention rate of hydrogen absorption capacity is 95.1 % after 30 cycles, which far exceeds the 65.5 % retention rate observed in milled MgH2. These property enhancements can be attributed to the presence of nano-sized Ni and its in situ derived Mg2Ni intermediate phases, which create more channels for hydrogen atoms diffusion. Meanwhile, the close contact between nano-Ni and the Mg/MgH2 matrix can provide active catalytic sites and low-energy interfaces for facilitating hydrogen adsorption and desorption. Our study presents a promising approach to significantly improve the hydrogen storage performance of MgH2 by modulating size-dependent catalytic activity.

Modification of the hydrogen compression properties of Zr–Fe–Cr–V-based alloys through Ti doping

Hydrogen refueling stations typically rely on compressors to increase the pressure of hydrogen received from long-tube trailers, enabling efficient refill of hydrogen storage tanks. However, mechanical hydrogen compressors are unable to effectively harness residual hydrogen below 6 MPa in long-tube trailers. Herein, we developed a ZrFe2-based hydrogen compression alloy to enhance the hydrogen pressure that meets the input pressure requirement of mechanical hydrogen compressors. Specifically, the co-substitution of Cr and V for Fe was conducted to reduce the plateau slope and hysteresis, and Ti was introduced to partially substitute Zr to regulate the plateau pressure. The effects of Ti on the structure and hydrogen storage properties of Zr–Fe–Cr-based alloys have been investigated by first-principles calculations, wherein Zr1-xTixFe1.7Cr0.2V0.1 (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were designed and synthesized. The optimized Zr0.8Ti0.2Fe1.7Cr0.2V0.1 alloy provided a hydrogen absorption capacity of 1.22 wt% under 3.88 MPa H2 pressure at 300 K and achieved an effective hydrogen compression capacity of 1.07 wt% at 355 K at an H2 desorption pressure of 6.36 MPa. This advancement holds great promise for the efficient utilization of residual hydrogen at approximately 6 MPa in long-tube trailers, thus leading to a significant improvement in hydrogen transportation efficiency.

Efficient hydrogen absorption and dehydrogenation of synergistically catalyzed Mg10Fe by MoS2 and Y2O3 via one-step synthesis and multistage regulation

To effectively deal with the long preparation period and low hydrogen absorption capacity issue of Mg-based hydrogen storage materials. One-step multistage control strategy and high-pressure hydrogenation have been employed to prepare Mg10Fe-M (M = MoS2 or Y2O3 or both) composites. The phase composition, microstructure, morphology, non-isothermal dehydrogenation thermodynamics and isothermal dehydrogenation kinetics at different milling time (2, 4, 8 h) were explored, and the catalytic hydrogen absorption and discharge mechanism of Mg10Fe–MoS2–Y2O3 was proposed. The addition of MoS2 nanoflowers and Y2O3 powder can synergistically regulate and improve the hydrogenation capacity and dehydrogenation temperature of Mg10Fe. The hydrogen absorption and dehydrogenation of Mg10Fe–MoS2–Y2O3 in short time milling for 2 h are 3.64 wt% and 3.27 wt% respectively. After extending the milling time to 8 h, the thermodynamic and kinetic behavior of Mg10Fe-M (M = MoS2 or Y2O3 or both) is greatly improved. Kinetically, the hydrogenation or dehydrogenation capacity increases significantly, Mg10Fe–MoS2 doesn't need activation, and the hydrogenation capacity reaches 5.42 wt% at 623 K, with a yield of about 85.9 % in 60 min. Thermodynamically, the initial dehydrogenation peak temperature drops to about 310 °C, and the apparent activation energy also decreases significantly, among which Mg10Fe–MoS2–Y2O3 was 91.87 kJ/mol. These are attributed to the fact that MoS2 nanoflowers provide many active sites for H2 adsorption and H atom dissociation. Synchro-efficient synthesis and regulation of Mg-rich composite hydrogen storage materials are expected to shorten the synthesis cycle, improve the hydrogen storage performance, and lay a material foundation for the design and development of solid hydrogen storage devices.

Identification of a Ternary Nitride Ti10Cu3N4 with a Unique Structure Type.

This study presents the synthesis and detailed structural analysis of the ternary nitride Ti10Cu3N4. Initially identified as Ti3CuN within the Ti-Cu-N ternary phase diagram, its crystal structure remained unresolved and was characterized solely as belonging to the tetragonal crystal system. Through a comprehensive structural analysis, this study proposes a revised stoichiometry as Ti10Cu3N4; its crystal structure represents a previously unreported structure type within the P4 2 /mnm space group. Its atomic arrangement was elucidated through a combination of X-ray powder diffraction profile analysis and density functional theory calculations, corroborated by neutron diffraction studies. Furthermore, the hydrogen storage properties of Ti10Cu3N4 were characterized, demonstrating a hydrogen absorption capacity of approximately 0.6 wt % with desorption occurring in the temperature range of 200-550 °C.

Effect of phase composition and cluster structure on de-/hydriding kinetics of as-cast and heat-treated Ti33V37Mn30-xCrx alloys

To enhance the hydrogen storage property, elements Mn in Ti33V37Mn30 alloy were partially substituted with varying concentrations of elements Cr. The Ti33V37Mn24Cr6 variant, which exhibited superior performance, was selected for further analysis. Ti33V37Mn24Cr6 samples were first heat-treated separately at 773K, 973K and 1173K for 2h, and then water-quenched. The effect of Cr substitution and heat treatment on the microstructure and de-/hydriding properties of Ti33V37Mn30-xCrx alloys were investigated. As-cast alloys were composed of BCC phases mainly, along with some C14 Laves phases and Ti-rich phases. The lattice parameter of BCC phases in Ti33V37Mn24Cr6 increased to 3.053 Å. Cr substitution changed the tetrahedral gap of the alloy. At 298K, the initial hydrogen absorption capacity and the maximum hydrogen desorption capacity of Ti33V37Mn24Cr6 were raised to 3.07 wt% and 1.81 wt%, respectively. The lattice parameter of Ti33V37Mn24Cr6 alloys heat-treated at 773K also enlarged to 3.056 Å. Elevating the heat treatment temperature to 973K and 1173K significantly raised the proportion of C14 Laves phases in the alloy. Hydrogen storage performance of heat-treated alloys was examined at 298K. The results suggested that the heat-treated alloys could be fully activated after one hydrogen ab-/desorption cycle. Ti33V37Mn24Cr6 alloy heat-treated at 773K achieved the maximum hydrogen desorption capacity of 1.83 wt%, with an accelerated hydrogen ab-/desorption rate.

Experimental investigation of the hydrogen storage capacity in LaNi3.6Al0.4Mn0.3Co0.7 alloy

The development of efficient and safe hydrogen storage technologies is essential for the large-scale use of hydrogen as an energy source. Metal hydride compounds, such as LaNi5 are suitable for hydrogen storage. This study investigates the hydrogen storage properties of the LaNi3·6Al0·4Mn0·3CoO.7 metallic powder, focusing on the influence of temperature and pressure on its hydrogen absorption capacity. The compound was characterized by structural and thermal methods. XRD diffraction confirmed the formation of multiphase LaNi5, La2Ni3 and also the presence of very small amounts of free Ni phase, while FTIR spectroscopy identified the vibrational modes and provided information on the functional groups and chemical bands present in the sample. SEM showed the morphology and grain size distribution of the compound. DSC measurements were used to determine the specific heat capacity. Hydrogen adsorption-desorption isotherms were measured across a temperature range from Tfluid = 20 °C to Tfluid = 40 °C, with an applied hydrogen pressure of 15 bar. The findings revealed that the LaNi3·6Al0·4Mn0·3CoO.7 alloy exhibited its highest hydrogen absorption capacity, approximately 9.3 g/kg, at Tfluid = 15 °C. Furthermore, experimental investigations were conducted to analyze the influence of temperature and hydrogen pressure on the absorption quantity.

Correlation between hydrogen absorption capacity and microstructure of Fe-rich Sm-Co-Fe-Cu-Zr permanent magnetic alloys

The correlation between hydrogen absorption capacity (HAC) and the microstructure of Sm26.2CobalFexCu4.0Zr2.3 (x = 23 wt%, 25 wt%, 27 wt%, 30 wt%) ingots and cast strips was systematically investigated. As the temperature rises from 373 to 423 K, the activation time, hydrogen absorption time and HAC of the Sm26.2CobalFe23Cu4.0Zr2.3 ingot decrease by 14.4%, 14.1%, and 19.3%, respectively. Dispersed 1:5 phase provides more channels for hydrogen diffusion, which is the main reason that HAC increases with the x increasing. The HAC of the same compound strips increases as the particles size of the pre-crushed decreases. However, no further embrittlement behavior appears in pre-crushed strips, which reaches an equal HAC as ingots. Micro-computerized tomography reveals that ingots contain small spherical-like holes and large flake micro-cracks, whereas strips mainly contain elliptical pores. The effects of grain size and inner defects size on structure stability were invested by Abaqus. Simulation results reveal that the superior embrittlement behavior of the ingots is predominantly influenced by the presence of large flake-like micro-cracks.

The study of La and Mg elements on the improved structure and hydrogen storage performance of Ca2MgNi9 alloy

In order to improve the comprehensive hydrogen storage performance of AB3-type (RE/Ca)-Mg-Ni alloys, a new series of Ca(Ca0.75La0.25)2-xMgxNi9 (x = 0.8, 0.9, 1.0, 1.1, 1.2) alloys is designed and prepared. Based on the as-cast Ca2MgNi9 alloy, La is introduced, and the ratio of rare earth (RE) to Mg is adjusted using the induction melting method. This alteration modifies the microstructure of the alloy and significantly enhances its hydrogen storage performance. The effects of microstructure on hydrogen storage performance and mechanism are analyzed. The phase composition and lattice parameters of the main phase are regularly regulated by appropriate element substitution. The lattice parameter of the main phase is increased, the capacity and kinetics of hydrogen storage are significantly improved. The initial hydrogen absorption capacity of the alloy increases from 1.744 wt% for Ca2MgNi9 to 1.975 wt% for Ca(Ca0.75La0.25)1.2Mg0.8Ni9 alloy. Furthermore, the synergistic regulation of La and Mg elements can increase the hydrogen desorption ratio and crystal structure stability of the alloy. This leads to the concurrent enhancement of effective hydrogen storage and cycle performance of the Ca2MgNi9 hydrogen storage alloy. The retention rate of hydrogen absorption capacity for the 50th cycle is increased from 77.13% for Ca2MgNi9 to 84.26% for Ca(Ca0.75La0.25)0.8Mg1.2Ni9. At the same time, owing to the adjustment of the cell volume and phase composition, the platform pressures of hydrogen absorption and desorption of the alloy have also experienced a multi-fold increase between 0.002 and 0.5 MPa at 303 K. This enhancement is advantageous for expanding the potential applications of this type of alloy. This work presents new ideas for enhancing the hydrogen storage performance of Ca2MgNi9 hydrogen storage alloys.

Porous Silicone Rubber Composite Supported 1,4-Diphenylethynyl Benzene for Hydrogen Absorption with Pd/C Catalyst.

Hydrogen is a dangerous gas as it reacts very easily with oxygen and may explode; therefore, the accumulation of hydrogen in confined spaces is a safety hazard. Composites consisting of unsaturated polymers and catalysts are a common getter, where the commonly used polymer is 1,4- diphenylethynyl benzene (DEB). Silicone rubber (SR) is a good carrier for hydrogen-absorbing materials due to its excellent chemical stability and gas permeability. In this work, polysiloxane, water, and a emulsifier are ultrasonically injected into a uniform emulsion, and the hydrogen getter DEB-Pd/C (Palladium on carbon) is then added. Under the catalysis of platinum (Pt), the cross-linking agent undergoes a hydrosilylation reaction to cross-link polysiloxane in emulsion to form silicone rubber. Then, the water was removed by freeze-drying, and the loss of water constructed a porous frame structure for silicone rubber, thus obtaining porous silicone rubber. The difference in hydrogen absorption performance between porous silicone rubber and ordinary silicone rubber was compared. It was found that, with the increase in water in the emulsion, the porous frame of silicone rubber was gradually improved, and the hydrogen absorption performance was improved by 243.4% at the highest, almost reaching the theoretical saturated hydrogen absorption capacity. Porous silicone rubber was prepared by emulsion mixing, which provided a new idea for further improving the hydrogen absorption performance of silicone rubber.

Experimental investigation on hydrogen transfer in coupled metal hydride reactors for multistage hydrogen purification application

Three stage metal hydride hydrogen separation system was tested, wherein each stage was configured with 1.2 kg of LaNi4.7Al0.3, LaNi5 and La0.9Ce0.1Ni5, placed in descending order of their equilibrium bed pressure respectively as R1 (La0.9Ce0.1Ni5) > R2 (LaNi5) > R3 (LaNi4.7Al0.3). Hydrogen absorption capacity obtained for R1, R2 and R3 were 15.91 g, 15.93 g and 16.02 g respectively for 3rd activation cycle, performed at 30 bar and 25 °C. For coupled reactor operation, optimum hydrogen transfer was for desorbing reactor at 90 °C and absorbing reactor at 20 °C, which was 12.31 g for R1 to R2 in 350 s, 13.33 g for R2 to R3 in 300 s and 13.38 g for R1 to R2 in 280 s, constituting to 1.03, 1.11 and 1.12 wt% of hydrogen storage respectively. Further, the system was tested for hydrogen purification, wherein inlet sample with 80% impurity (18% Ar, 20% CO2, 20% N2, 20% CH4 and 2% CO) and 20% H2 was used for purification study. According to Thermal Conductivity Detector (TCD) results, the system delivered 91.54%, 99.996% and 99.9999% pure hydrogen respectively for stage 1, stage 2 and stage 3 purification. The system works within low temperature range of 20–90 °C.

Effects of differential speed rolling and H2S poison on hydrogen storage performance of ZK60 alloys ball-milled with C, Pd, Ag, and Zr

The commercial ZK60 magnesium alloy was used to investigate hydrogen absorption performance. The ZK60 alloy was severely deformed via differential speed rolling with differential speeds of 6:3 and 9:3. High energy ball milling was used to blend deformed ZK60 powder with 5 wt% activated carbon(C), 0.5 wt% silver (Ag), 0.5 wt%palladium (Pd), and 1 wt% zirconium (Zr) for 20h at 1725 rpm. Hydrogen absorption characteristics at different low temperatures and number of cycles were analyzed using Sievert's apparatus with hydrogen supplied with H2S impurities. The microstructure of the powder was analyzed field emission scanning electron microscope (FESEM). The hydrogen absorption capacity increases with the temperature rise, and maximum capacity(6.02 wt%) was observed in 5C1Zr deformed at 9:3DSR at 200 °C after five cycles. Hydrogen absorption capacity increases after each hydrogenation cycle in 5C0.5Ag and 5C1Zr but remains the same in 5C0.5Pd. The increase in H2S concentration decreases the hydrogen capacity, and increase in the number of cycles further deteriorates absorption capacity when the differential speed ratio is 6:3. The H2S concentration variation has almost no effect at the differential speed of 9:3. The maximum hydrogen absorption kinetics (74.7%) in 10min was observed in 5C1Zr. A more refined dendritic microstructure was observed in ZK60 alloy deformed with a differential speed ratio of 9:3.

Additively Manufactured Silicone Polymer Composite with High Hydrogen Getter Content and Hydrogen Absorption Capacity.

Hydrogen getters consisting of 1,4-bis[phenylethynyl] benzene (DEB) and a carbon-supported palladium catalyst (Pd/C) have been used to mitigate the accumulation of unwanted hydrogen gas in a sealed system. Here, we report the formulation of a composite resin consisting of silicone polymer plus DEB-Pd/C as an active getter material and the additive manufacturing of silicone getter composites with a high getter content (up to 50 wt %). NMR and DSC studies suggest no reaction between the silicone polymer resin and DEB even at elevated curing temperatures (75 °C). Getter composites with varying amounts of getter and filler were formulated, and their rheological properties were studied. The two composite resins with good printability parameters and different getter contents were chosen to make 3D-printed samples. The hydrogen absorption capacity of these samples was studied at a low hydrogen pressure of 750 mTorr of pure hydrogen. The getter composite with 50 wt% of getter showed normalized DEB conversion of 83%, with the hydrogen adsorption capacity of 100.2 mL of H2 per gram of polymer getter composite.

Influence of Zr Addition on the Microstructure and Hydrogenation Kinetics of Ti50-xV25Cr25Zrx (x = 0, 5, 7, and 9) Alloys.

Due to the poor activation performance and kinetics of Ti50V25Cr25 alloys, the element Zr was added to improve the phase structure of the alloy and achieve a high-performance hydrogen storage alloy. The Ti50-xV25Cr25Zrx (x = 0, 5, 7, and 9) system alloys were prepared by arc melting. The alloys were analyzed using an X-ray diffractometer (XRD), scanning electron microscope (SEM), and differential scanning calorimeter (DSC). The hydrogen storage capabilities of the alloys were also obtained by the Sievert volumetric method. The results indicated that the alloy with Zr added had a combination of the C15 Laves phase and the BCC phase, whereas the Zr-free alloy had a BCC single phase. The partial replacement of Zr with Ti resulted in an increase in the lattice parameters of the main phase. The hydrogen storage kinetic performance and activation of the alloys both significantly improved with an increasing Zr concentration. The time to reach 90% of the maximum hydrogen storage capacity decreased to 2946 s, 230 s, and 120 s, respectively, with the increases in Zr concentration. The initial hydrogen absorption content of the alloys increased and then decreased after the addition of the element Zr. The second phase expanded with an increasing Zr concentration, which in turn decreased the abundance of the BCC main phase. The Ti43V25Cr25Zr7 alloy showed good cycle stability and hydrogen-desorption performance, and it could absorb 90% of the maximum hydrogen storage capacity in around 230 s. The maximum hydrogen-absorption capacity of the alloy was 2.7 wt%. The diffusion activation energy of hydrogen desorption dropped from 102.67 kJ/mol to 92.62 kJ/mol.

Highly air-stable magnesium hydrides encapsulated by nitrogen-doped graphene nanospheres with favorable hydrogen storage kinetics

Severe surface oxidation and sluggish kinetic rates of Mg hydrides (MGHs) are the main bottlenecks for their industrial applications. Herein, we present a strategy to simultaneously tackle these problems. The nano-size MGHs were encapsulated in nitrogen-doped graphene nanospheres (NGNSs) via a facile wet-chemical method. This configuration not only prevented the MGHs from oxidation when exposed to air even after a long duration, but also stimulated faster kinetic rates of hydrogen absorption and desorption owing to the nano-size effect of MGHs and the unique electronic structure of NGNSs. As a result, MGHs of ca. 20 nm were coated by a few layered NGNSs to form MGH@NGNSs nanocomposite. A high hydrogen absorption capacity of 6.5 wt% was achieved at 200 °C within 0.4 h, with a releasing hydrogen capacity of 5.5 wt% at 300 °C within 0.5 h, indicating that this composite has obtained remarkably hydrogen storage performance. Density Functional Theory (DFT) based calculations suggested that the hydrogen adsorption/desorption kinetics were significantly fast at the interface of Mg surface and NGNSs with pyridinic configuration. This strategy paves a way for the development of high-performance Mg-based hydrogen storage materials for industrial applications.

Microstructure and gas-solid hydrogen storage properties of La1-xCexY2Ni10.95Mn0.45 (x = 0 – 0.75) alloys

RE-Y-Ni-based superlattice alloys have been studied for their high hydrogen storage capacity and excellent activation properties. However, their practical applications in gas-solid hydrogen storage devices are limited by their low hydrogen absorption/desorption platform pressure and the occurrence of a double platform phenomenon. In this study, we investigated the phase structure and gas-solid hydrogen storage properties of La1−xCexY2Ni10.95Mn0.45 (x = 0, 0.15, 0.30, 0.45, 0.60, 0.75) alloys. As the Ce content increases, the content of Ce2Ni7 phase and the platform pressure also increase, while the hydrogen storage capacity and hydrogen desorption enthalpy decrease. When the Ce content increases to 0.45, the Gd2Co7 phase disappears and the LaNi5 phase appears, the hydrogen absorption/desorption platform of the alloy changes from a double platform to a single platform. However, the increase in Ce content leads to a higher amount of residual hydrogen during the dehydrogenation process, attributed to the increased content of the Ce2Ni7 phase. The La0.55Ce0.45Y2Ni10.95Mn0.45 alloy exhibits a hydrogen absorption capacity of 1.61 wt%, with a capacity retention of 97.89% after 100 cycles, and achieves a hydrogen desorption platform pressure of 0.23 MPa. These results indicate that this alloy demonstrates the best overall hydrogen storage performance, characterized by high platform pressure and hydrogen storage capacity.

Composition optimization and hydrogen storage properties of Ti–V–Mn–Fe alloys

Ti–V-based hydrogen storage alloys have garnered interest owing to their salient advantages of reversible hydrogen absorption/desorption at room temperature and excellent kinetic properties. However, the complicated smelting technology of high-purity V metal renders expensive prices, hampering their large-scale production and application. Herein, to overcome this hurdle, abundant and inexpensive Mn and Fe are added to obtain Ti–V–Mn–Fe hydrogen storage alloys. The novel alloy compositions were obtained using a uniform design method. The hydrogen absorption/desorption behaviors of alloys prepared using arc melting technology were analyzed in detail. Systematic investigations show that the activation, kinetics, and thermodynamic properties of alloys are closely correlated with the Ti/(Mn + Fe) ratios. The designed alloy compositions have a multiphase structure with a body-centered cubic (BCC) main phase. The lattice parameters of the BCC phase increase with increasing Ti/(Mn + Fe) ratio, and the large lattice parameters of alloys are beneficial to facilitate the diffusion of hydrogen atoms, resulting in fast kinetics. A reasonable Ti/(Mn + Fe) ratio positively affects the hydrogen storage properties. Among them, the Ti40V40Mn2Fe18 alloy with Ti/(Mn + Fe) = 2 achieved a hydrogen absorption capacity of 3.472 wt% at 298 K and an effective reversible hydrogen storage capacity of 1.485 wt% above 0.1 MPa at 363 K. This study provides a novel insight for designing Ti–V-based alloy compositions via the uniform design method.