Hydrogen Storage Alloys Research Articles

A review of body-centered cubic-structured alloys for hydrogen storage: composition, structure, and properties

A review of body-centered cubic-structured alloys for hydrogen storage: composition, structure, and properties

Effect of Equivalent La and Ce Substitution for Y on the Structure and Properties of A2B7-Type La–Y–Ni-Based Hydrogen Storage Alloys

Effect of Equivalent La and Ce Substitution for Y on the Structure and Properties of A₂B₇-Type La–Y–Ni-Based Hydrogen Storage Alloys

Enhanced long cycling durability of Ce2Ni7-type single-phase Sm–Mg–Ni-based hydrogen storage alloys for nickel metal hydride batteries

La–Mg–Ni-based superlattice structure alloys are promising negative material candidates for nickel metal hydride (Ni-MH) batteries, but their application is challenged by cycling life. Herein, we propose Sm–Mg–Ni-based alloys beyond La–Mg–Ni-based alloys to promote long-term durability. Specifically, Ce2Ni7-type single-phase Sm0.58La0.25Mg0.17Ni3.26Al0.18 and Sm0.54La0.29Mg0.17Ni3.26Al0.18 alloys have been obtained, delivering significantly high-capacity retention rates over 70 % after 500 cycles at a 1C charge and discharge rate. Furthermore, the alloy's discharge ability has been optimized via manipulating Sm/La ratios, of which its effect on the structure and electrochemical properties is detailly studied. It is found that the discharge capacity of the Sm0.58La0.25Mg0.17Ni3.26Al0.18 alloy with a higher Sm/La ratio outperforms the Sm0.54La0.29Mg0.17Ni3.26Al0.18 alloy. However, the low Sm/La ratio Sm0.54La0.29Mg0.17Ni3.26Al0.18 alloy is favorable for discharge ability at a high-rate current rate and features lower plateau pressure and enthalpy change compared with Sm0.58La0.25Mg0.17Ni3.26Al0.18. The work is expected to offer new insights into the composition design of hydrogen storage alloys with long cycling life for Ni-MH batteries.

Prediction of the optimal hydrogen storage in high entropy alloys

Hydrogen is the most abundant element in nature, characterized by its vast resources, recyclability, and environmentally friendly. Also, it can exist in various forms, such as gas, liquid, or solid, to meet different storage needs. In solid-state storage, the hydrogen storage alloys have received widespread attention due to hydrogen is stored in the form of hydrides. In recent years, high entropy alloys (HEAs), as a new type of novel alloy design concept have attracted a lot of attention in many fields including hydrogen storage due to their unique structures and excellent properties. Moreover, the freedom of element selection leads to various types of HEAs, further enhancing the potential for their application in hydrogen storage. This article focuses on the hydrogen storage performance of HEAs and provides a comprehensive overview of the hydrogen storage mechanism, thermodynamics, and kinetics. Additionally, we summarize and compare the hydrogen storage capacities of previously published HEAs and introduce two empirical parameters, valence electron concentration (VEC) and atomic size difference (δ), and their relationship with hydrogen storage capacity. By applying the K-means clustering algorithm, we conclude that the optimal hydrogen storage capacity of HEAs occurs when 4 <VEC < 6 and 5.3 % <δ < 7.5 %. This finding offers valuable guidance for the future design of efficient hydrogen storage HEAs.

Effect of Nb on hydrogen storage properties of Ti–V–Cr-based alloys

This research investigates the impact of incorporating Nb into Ti–V–Cr-based alloys, with compositions ranging from Ti30-xV35Cr35Nbx (x = 0, 5, 10, 15, and 20 at. %), with the objective of enhancing hydrogen storage properties. Employing a comprehensive approach encompassing design, synthesis, and characterization, the study aimed to develop novel hydrogen storage alloys. Utilizing the CALPHAD method, the alloys were designed to anticipate the formation of multicomponent single-phase structures. Structural and microstructural analyses of the synthesized alloys were conducted using XRD, SEM, and EDS techniques. The hydrogen storage capabilities were evaluated utilizing a Sieverts’ type apparatus. The investigated alloys displayed a singular-phase BCC solid solution, characterized by dendritic microstructures. Notably, the Nb-free alloy, Ti30V35Cr35, demonstrated the highest hydrogen storage capacity, reaching 3.62 wt% (∼1.9 H/M) under 20 bar of H2 at room temperature. Among the Nb-containing alloys, Ti25V35Cr35Nb5 exhibited a capacity of 2.91 wt% (∼1.6 H/M) under identical conditions. Furthermore, the incorporation of Nb up to 10 at. % effectively bolstered cycle durability. This study underscores the presence of an optimal Nb content crucial for achieving the highest hydrogen capacity and cycle durability in these alloys.

Utilization of Hydrogen Using Hydrogen Storage Alloys

Utilization of Hydrogen Using Hydrogen Storage Alloys

Anti-oxidation effect of chromium addition for TiFe hydrogen storage alloys

Anti-oxidation properties of Cr substitution were investigated by comparing TiFe and TiFe0.9Cr0.1. Kinetic measurements reveal that the degradation rate of TiFe0.9Cr0.1 is slower than that of TiFe, indicating that Cr substitution drastically enhances the anti-oxidation properties of the mother alloy TiFe. In order to understand the mechanism of this effect, X-ray photoelectron spectroscopy (XPS) was used to identify the surface chemical state of these alloys, which indicates that Cr plays quite an important role in the suppression of surface oxidation. It is clarified that the deactivation of TiFe is caused by the oxidation of Ti on the surface and, as a result, the obstruction of hydrogen penetration. On the contrary, with the substitution of Cr for Fe in TiFe0.9Cr0.1, the Ti oxidation becomes more difficult even though the Cr was totally oxidized, which makes it easier to keep the initial activated state of hydrogenation (Ti with a low oxidation state). It also further demonstrated that Cr acts as a sacrificial element, undergoing complete oxidation to protect Ti from oxidation, and assists in keeping metallic Ti0, which is crucial for maintaining the hydrogen absorption kinetics. Therefore, the Cr substitution for Fe significantly improves the anti-oxidation properties of TiFe-based alloys.

Design of air-stabilized Mg-Sc alloy with enhanced hydrogen storage properties via in-situ formation of Sc-hydride in Sc dissolved phase

Severe surface oxidation and slow kinetic rates are the main obstacles which limit the industrial application of Mg-based hydrogen storage alloys. In this work, an attempt is carried out to design and develop the highly active and air-stabilized Mg-Scx (x = 1, 2 and 3 at.%) alloys via an inexpensive and efficient method. The Sc atoms are completely dissolved in the Mg matrix to form single-phase solid solution alloy. At 325 °C and 2.0 MPa hydrogen pressure, Mg-Sc2 alloy exhibits the rapidest absorption rate with the hydrogen capacity of 6.25 wt%. The synergism of lattice distortion induced by Sc-doping and the in-situ formed ScH2 nanoparticles enhance the de/hydrogenation kinetics. After exposed to air for 800 h, almost no MgO can be detected and the hydrogen storage capacity is only reduced by 0.11 wt%, maintaining the initial total capacity more than 98 %. Sc can protect Mg-based alloys from O2 and H2O pollution, which is ascribed to the formation of an oxygen atoms exclusion zone around the solute atoms caused by valence electrons transfer.

The design of Mg–Ti–V–Nb–Cr lightweight high entropy alloys for hydrogen storage

In this study, body-centered-cubic Ti24V18Nb6Cr12 high entropy alloy (HEA) is selected as the matrix to design Mg–Ti–V–Nb–Cr lightweight HEAs. Based on first-principles calculations, the hydrogen storage properties of a series of Mg–Ti–V–Nb–Cr HEAs are systematically investigated. The designed Mg-based HEAs are found to be stable after hydrogenation and exhibit high gravimetric hydrogen storage capacities (HSCs). Particularly, the gravimetric HSC of Mg6Ti24V18Cr12 HEA is as high as 4.091 wt%. Besides, the dehydrogenation temperature of the Mg–Ti–V–Nb–Cr HEAs decreases obviously with increasing Mg content, which results from the weakened bonding strength of <M-H> pairs. This study demonstrates that the Mg6Ti24V18Cr12 HEA is a potential candidate for hydrogen storage.

Development of Ti–Zr–Mn–Cr-(V–Fe) based alloys for hydrogen feeding system in hydrogen metallurgy application

AB2-type Ti-based hydrogen storage alloys are considered promising candidates for the hydrogen feeding system in hydrogen-metallurgy application. In this work, Ti0·87Zr0.15MnxCr1.75-xV0.25 (x = 1.25–1.5), Ti0·87Zr0·15Mn1·5Cr0.5-y(VFe)y (y = 0.25–0.43) and Ti0.85+zZr0.15Mn1·5Cr0·07(VFe)0.43 (z = 0–0.05) alloys were synthesized using induction levitation melting, where ferrovanadium VFe consists of 80 wt% V and 20 wt% Fe. Subsequently, their microstructures and hydrogen storage performances were systematically investigated. The results demonstrate that all alloy samples exhibit a single C14 Laves phase structure with uniform element distribution. With the increment of Cr/Mn, VFe/Cr ratio, or Ti stoichiometry, the alloys exhibit enhanced hydrogen storage capacity, accompanied by a decrease in hydrogenation equilibrium pressure because of interstitial volume expansion or hydrogen affinity improvement, which is also supported by density functional theory calculations. Considering the application of hydrogen metallurgy, Ti0·86Zr0·15Mn1·5Cr0·07(VFe)0.43 alloy is regarded as a promising candidate, exhibiting a saturated capacity of 2.01 wt% H2, an effective reversible capacity of 1.91 wt% H2, rapid hydrogenation kinetics, excellent cyclic durability and low costs. This work provides valuable insights into the compositional design of hydrogen storage alloys for the hydrogen feeding system in hydrogen metallurgy applications.

An Investigation on the Potential of Utilizing Aluminum Alloys in the Production and Storage of Hydrogen Gas.

The interest in hydrogen is rapidly expanding because of rising greenhouse gas emissions and the depletion of fossil resources. The current work focuses on employing affordable Al alloys for hydrogen production and storage to identify the most efficient alloy that performs best in each situation. In the first part of this work, hydrogen was generated from water electrolysis. The Al alloys that are being examined as electrodes in a water electrolyzer are 1050-T0, 5052-T0, 6061-T0, 6061-T6, 7075-T0, 7075-T6, and 7075-T7. The flow rate of hydrogen produced, energy consumption, and electrolyzer efficiency were measured at a constant voltage of 9 volts to identify the Al alloy that produces a greater hydrogen flow rate at higher process efficiency. The influence of the electrode surface area and water electrolysis temperature were also studied. The second part of this study examines these Al alloys' resistance to hydrogen embrittlement for applications involving compressed hydrogen gas storage, whether they are utilized as the primary vessel in Type 1 pressure vessels or as liners in Type 2 or Type 3 pressure vessels. Al alloys underwent electrochemical charging by hydrogen and Charpy impact testing, after which a scanning electron microscope (SEM) was used to investigate the fracture surfaces of both uncharged and H-charged specimens. The structural constituents of the studied alloys were examined using X-ray diffraction analysis and were correlated to the alloys' performance. Sensitivity analysis revealed that the water electrolysis temperature, electrode surface area, and electrode material type ranked from the highest to lowest in terms of their influence on improving the efficiency of the hydrogen production process. The 6061-T0 Al alloy demonstrated the best performance in both hydrogen production and storage applications at a reasonable material cost.

Design, Synthesis, and Characterization of Al‐Containing Multicomponent Alloys for Hydrogen Storage and Compression

AbstractIn this paper, compositions within the TiZrAlCrMn, TiZrAlCrFe, and TiZrAlMnFe alloy systems that form the C14 Laves phase are investigated. The design, synthesis, structural, and hydrogen storage characterizations for an equiatomic and a non‐equiatomic composition for each alloy system are presented. Additionally, the further development of a thermodynamic method for the calculation of pressure‐composition‐isotherms (PCIs) is presented of C14 Laves phase alloys that absorb hydrogen by solid solution. Overall, the results shown in this paper indicate that Al‐containing multicomponent alloys can present promising hydrogen storage performance under high pressures. Nonetheless, high concentrations of aluminum in highly concentrated (equiatomic) alloys can have a negative impact on the hydrogenation properties. The Ti0.29Zr0.05Al0.05Cr0.26Mn0.35 composition showed promising hydrogenation/dehydrogenation properties. The gravimetric capacity of this alloy is ≈1.76 wt.% H2 and the PCIs measured indicate that this material has potential for high‐pressure hydrogen storage and compression applications. The use of the presented thermodynamic model for the design of multicomponent alloys is suggested.

Improving oxygen resistance of hydrogen storage alloys with graphite or nickel coating

A series of graphite- and Ni-coated hydrogen storage alloys were prepared with simple ball-mill method, and their hydrogen storage behaviors were characterized and compared with bare alloys. The results showed that the oxygen resistance of the graphite-coated materials increased, while the hydrogen storage kinetics decreased significantly. For the Ni-coated materials, oxygen resistance was noticeably improved and excellent oxygen resistance was achieved with sufficient Ni loading, while the hydrogen storage capacity and kinetics were also maintained or even improved. Our results show that the elemental coating method is an effective method to improve the oxygen resistance of hydrogen storage alloys, which brings about new insights into the design of these materials.

Electrochemical Performances of MgAlTiCoNi Hydrogen Storage Alloy used as Electrode

Electrochemical Performances of MgAlTiCoNi Hydrogen Storage Alloy used as Electrode

Vanadium-based alloy for hydrogen storage: a review

Vanadium-based alloy for hydrogen storage: a review

Phase structure and electrochemical properties of A5B19 La0.8-xPrxMg0.2Ni3.8 (x = 0–0.3) hydrogen storage alloy anode material

The La0.8-xPrxMg0.2Ni3.8 (x = 0, 0.05, 0.1, 0.2, 0.3) alloy were synthesized useing the induction melting method. X-ray diffraction, scanning electron microscope, electron probe micro analyzer, and electrochemical tests were used to analyze the structure and electrochemical performance of the La0.8-xPrxMg0.2Ni3.8 (x = 0–0.3) alloy. It was studied how the Pr element affected the electrochemical characteristics and microstructure of the A5B19 La-Mg-Ni based hydrogen storage alloy. The results show that the alloy consists of the CaCu5-LaNi5 phase, 2 H-Pr5Co19 phase, and 3R-Ce5Co19 phase. The abundance of the A5B19 phase increase with the increase of Pr content, while the abundance of the LaNi5 phase decrease, and the addition of Pr promotes the formation of the 2 H-Pr5Co19 phase. According to the results of the electrochemical test, every sample has good activation qualities, and the activation can be completed in 3–4 times. The activation properties are not significantly altered by the addition of Pr. The maximum discharge capacity increases at first, then decreases, reaching the highest 371.15 mAh g−1 at x = 0.2. The cyclic stability gradually improves with increasing content of Pr, and the maximum capacity retention rate reaches 85.80 % after 100 cycles. The primary factor influencing the alloy's high rate discharge ability is the exchange current density. With the increase of the exchange current density, the high rate discharge performance is gradually enhanced.

Effect of graphene addition on activation and kinetic properties of La–Mg–Ni-based hydrogen storage alloys

Effect of graphene addition on activation and kinetic properties of La–Mg–Ni-based hydrogen storage alloys

Effect of preparation routes on the performance of a multi-component AB2-type hydrogen storage alloy

This article presents experimental results on the preparation and characterisation of a multi-component AB2–type intermetallic hydrogen storage alloy (A = Ti0.85Zr0.15, B = Mn1.22Ni0.22Cr0.2V0.3Fe0.06). The alloy samples were prepared by induction melting using Y2O3-lined alumo-silica and graphite crucibles. The characterisation results were compared with the ones for the reference sample of the same composition prepared by arc melting. It has been shown that the induction-melted samples exhibit reduced hydrogen sorption capacities and sloping plateaux on the pressure composition isotherms (PCI’s). The origin of the observed effects has been shown to be in the inhomogeneity of the induction-melted alloys and their contamination due to crucible—melt interaction, particularly pronounced for the alloy melted in the alumo-silica crucible; this alloy was additionally characterised by the decrease of Zr/Ti ratio and, in turn, higher plateau pressures of the PCI’s.

Comprehensive improvement of AB2 hydrogen storage alloy: Substitution of rare earth elements for different A-side alloys

Rare earth substitution enhances the activation, absorption/desorption properties of hydrogen storage alloys, a crucial research area. Despite the extensive variety of A-site elements in multicomponent alloys, there remains a scarcity of reports on how to enhance the hydrogen storage capacity of alloys by substituting different elements with rare earth elements at the A-site, which needs to be further explored. In this study, the AB2 type Ti-Mn based hydrogen storage alloy was selected as the research object, and the effect of replacing different elements in the A-position by rare earth elements with equal atomic ratios was systematically analyzed by replacing the hydrogen absorption elements Ti/Zr with the rare earth metal Ce. The result reveals that Ce substitution significantly enhances the hydrogen storage and cyclic performance of the alloys, with Ce substituting for Ti showing superior performance. Theoretical calculations indicate that Ce substitution for Ti in alloys leads to lower formation energy and easier hydrogen absorption than Ce substitution for Zr. Beyond the influence of the Lundin’s theory, this work proposes for the first time that the difference in electronegativity between substituent elements may one of the crucial factors affecting the hydrogen storage performance of alloys. The greater difference in electronegativity may lead to a higher hydrogen storage capacity of the hydrogen storage alloy. This opens a new avenue for research into doping/substitution modifications of hydrogen storage alloy elements. These findings not only enrich the knowledge on element doping modification but offer valuable insights for future research on rare earth-doped modification of hydrogen storage alloys.

Optimization of V-Ti-Fe hydrogen storage alloy based on orthogonal experiments

Vanadium-based solid solution hydrogen storage alloys have attracted much attention because of their high hydrogen capacity, mild hydrogen absorption- desorption conditions, and high safety. However, the V-Ti-Fe alloys, developed at low cost, have a relatively low effective capacity and is unsuitable for practical production. In this work, (VxFe100-x)100-yTiy-z%Ce (x=0.83,0.85,0.87; y=16,18,20; z=1,2,3) alloys are designed by orthogonal method to investigate the effect of compositions on the microstructure and hydrogen storage properties. It is shown that the effective hydrogen capacity and desorption plateau pressure of the (VxFe100-x)100-yTiy-z%Ce alloy are related to multiple factors, such as lattice constants, tetrahedral interstitials of the BCC and BCT phases, electron concentration and Vickers hardness. The optimized alloy (V87Fe13)82Ti18-1 %Ce based on the orthogonal experiments shows a reversible hydrogen storage capacity of 2.17 wt% and a desorption plateau pressure of 0.373 MPa at 70°C. The reversible hydrogen capacity of (V87Fe13)82Ti18-1 %Ce is superior to most V-Ti-Fe alloys.