Electronic structure and hydrogen storage properties of Li–decorated single layer blue phosphorus

Single layer blue phosphorus (SLBP) is a promising two–dimensional material for nanoelectronic devices, but the electronic structure and hydrogen storage property of modified SLBP received little attention. Li atoms can be strongly bonded on SLBP in a 1:1 Li/P ratio with a binding energy larger than the cohesive energy of bulk Li. The geometric structure of SLBP suggests the 3s3p orbitals of the P atom hybridize in sp³ manner. But our analyses show that the 3s and 3p orbitals form bonding and antibonding orbitals respectively. The 3s orbitals are fully occupied as they have much lower energies, and the bonding orbitals formed by P 3p are occupied in pure SLBP. The decorated Li atoms transfer their 2s electrons to the antibonding orbital formed by P 3p. The Li atoms exist as +1 cations and they are ionically bonded on SLBP. H₂ molecules adsorbed on the Li⁺ cations are strongly polarized and form strong adsorption. When two H₂ are adsorbed on each Li atom decorated at the 1:1 Li/P ratio, the hydrogen storage capacity reaches 9.52 wt% but the H₂ molecules are arranged in two layers with the adsorption energy ?0.168 eV/H₂. When the Li atoms are decorated alternatively on the two sides of the P₆ rings with a Li/P ratio of 1:2, each Li atom can absorb two H₂ molecules in a single–layer; the hydrogen storage capacity is 5.48 wt% and the adsorption energy reaches ?0.227 eV/H₂. These results mean the Li–decorated SLBP can work at ambient temperature with high reversible hydrogen storage capacity.     

Structural characterization and hydrogen storage properties of MgH2–Mg2CoH5 nanocomposites

Mixtures of XMg–Co containing different amounts of Mg (X = 2, 3 and 7) were reactive milled under hydrogen atmosphere. 2Mg–Co only formed the Mg₂CoH₅ complex hydride, while the mixtures 3Mg–Co and 7Mg–Co formed different contents of Mg₂CoH₅ and MgH₂. Their structural features and hydrogen storage properties were analyzed by different techniques. In-situ synchrotron X-ray diffraction, combined with thermal analysis techniques, (differential scanning calorimetry, thermal gravimetric analysis and quadrupole mass spectrometer) was carried out to observe the behavior of the MgH₂–Mg₂CoH₅ mixtures during the first H-desorption. It was found that the presence of the Mg₂CoH₅ complex hydride has a beneficial effect on the first H-desorption of the MgH₂. Additionally, after first desorption, conventional hydrogenation under high pressure and high temperature of 3Mg–Co and 7Mg–Co samples led to the formation of the Mg₆Co₂H₁₁ complex hydride. The presence of Mg₆Co₂H₁₁ considerably impaired the desorption properties of the nanocomposites.     

Structural,electronic and spectral properties referring to hydrogen storage capacity in binary alloy ScBn (n = 1–12) clusters

Based on the DFT calculations within GGA approximation, we have systematically studied the ScB_n (n = 1–12) clusters and their hydrogen storage properties. The results show that the maximal adsorption for H₂ molecules is ScB₇ 6H₂ structure with the hydrogen storage mass fraction about 9.11%. For ScB_n·mH₂ clusters as n = 7 or 9–12, the average binding energies between 0.202 and 0.924 eV are suggestively conducive to hydrogen storage. In these medium clusters, the moderate adsorption strength can benefit application of hydrogen energy owning to easily adsorption and dissociation on H₂ molecules at room temperature and 1 bar pressure. Furthermore, the absorption spectrum is also investigated from TDDFT calculation. An obvious red-shift of spectral lines at 4.2 eV or 5.6 eV is detected with the increase of number of H₂ molecules. It can be regard as ‘fingerprint’ spectrum in experiment to indicate adsorption capacity of H₂ molecules for ScB_n·mH₂ nanostructures.     

Modification of nano-eutectic structure and the relation on hydrogen storage properties: A novel Ti–V–Zr medium entropy alloy

TiV-based alloys present desirable hydrogen storage properties owing to the formation of Body-centered cubic (BCC) solid solutions. However, the nanostructure that helps hydrogen absorption and desorption is hard to be designed and prepared in these alloys. In this study, Ti₄₀Zr_60-xV_x (x = 20, 25, 30) alloys with hyperfine nano-eutectic structures of 50–500 nm in lamellar space are prepared, and the nano-eutectic structures can be refined by increasing Zr content. Ti₄₀Zr_60-xV_x alloy powder exhibits excellent activation and hydrogenation properties. The phase separation and nano-eutectic structure are formed due to the differences of atomic size in Ti₄₀Zr_60-xV_x alloys. The highest total hydrogenation capacity of 2.4 wt% is obtained within 10 min at 200 °C under 1 MPa H₂ by Ti₄₀V₃₅Zr₂₅ alloy, surpassing that of Ti₄₀Zr₄₀V₂₀ and Ti₄₀Zr₃₀V₃₀ alloys of 2.2 wt% in 20min. Based on the Johnson-Mehl-Avrami-Kolmogorov (JMAK) model, lower energy is required for the hydrogenation of Ti₄₀V₃₅Zr₂₅ alloy. Due to the formation of some stable hydrides, the Ti₄₀Zr_60-xV_x alloys show lower reversible hydrogenation capacities. The spinodal decomposition in Ti₄₀V₃₅Zr₂₅ alloy facilitates the formation of reticular eutectics, which provide high-density phase interfaces and produce “synergistic effect”. As a result, the hydrogenation kinetic and capacity are enhanced significantly.     

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.     

A first principles study of hydrogen storage in lithium decorated defective phosphorene

In this study, we studied defect-engineering and lithium decoration of 2D phosphorene for effective hydrogen storage using density functional theory. Contrary to graphene, it is found that the presence of point-defects is not preferable for anchoring of H₂ molecules over defective phosphorene. According to previous research, strategies such as defect engineering, metal decoration, and doping enhance the hydrogen storage capacity of several 2D materials. Our DFT simulations show that point defects in phosphorene do not improve the hydrogen storage capacity compared to pristine phosphorene. However, selective lithium decoration over the defective site significantly improves the hydrogen adsorption capacity yielding a binding energy of as high as ?0.48 eV/H₂ in Li-decorated single vacancy phosphorene. Differential charge densities and projected density of states have been computed to understand the interactions and charge transfer among the constituent atoms. Strong polarization of the H₂ molecule is evidenced by the charge accumulation and depletion. The PDOS shows that the presence of Li leads to enhanced charge transfer. The maximum gravimetric density was investigated by sequentially adding H₂ molecules to the Li-decorated single vacancy defective phosphorene. The Li-decorated single vacancy phosphorene is found to possess a gravimetric density of around 5.3% for hydrogen storage.     

Theoretical studies of lithium–aluminum amid and ammonium as perspective hydrogen storage

A statistical theory of the phase transformation of lithium-aluminum amide with the release of ammonia has been developed. The free energies values of the phases were calculated, and their dependences on temperature, pressure, hydrogen concentration, and energy parameters were established. Phase diagram is built. The equations of the thermodynamic equilibrium state are calculated. The isoprocesses in the phases are investigated. The coefficients of squareness and uniformity of isotherms are obtained. The feature of the hydrogen concentration on temperature dependence in the phases has been established.     

Heat and gas transport properties in pelletized hydride–graphite-composites for hydrogen storage applications

Metal hydrides are suitable for the compact, efficient and safe storage of hydrogen. Considering hydride-based hydrogen storage tanks, the enhancement of the heat and gas transport properties of the hydride bed is crucial for increased (un-)loading dynamics of the tank.     

Oxide–nickel electrodes as hydrogen storage units of high-capacity

In this study, it was experimentally proved that during a Ni–Cd batteries long service life (more than five years), the hydrogen accumulation in large quantities takes place in a form of nickel hydrides in a sintered nickel matrix of oxide–nickel electrodes. The capacity of the sintered nickel matrix of the oxide–nickel electrode as a hydrogen absorber was quantified as 20.1 wt% and 400 kg m⁻³. These values exceed thrice all the earlier data obtained by traditional methods for any reversible metal hydride.     

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

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

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

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

Novel permeable material “yttrium decorated zeolite templated carbon” for hydrogen storage: Perspectives from density functional theory

The hydrogen storage capacity of a novel permeable material viz Yttrium (Y) decorated zeolite templated carbon (ZTC) has been investigated using ab-initio DFT based simulations. The study reveals that each Y atom bonded on ZTC can attach at the most of 7H₂ molecules with average binding energy of ?0.35 eV/H_2. The gravimetric hydrogen storage capacity of ZTC with full decoration of Y atom comes about to 8.61 wt% which is sufficiently higher than the limit of 6.5 wt% set by the energy department of the United States of America. The desorption temperature of the system is 437 K. The stability of the structure over such an elevated temperature has been ensured via molecular dynamics (MD) simulations. The stability of the structure at room temperature and presence of sufficient energy barrier for the diffusion of Y atom signifies that the chances of metal-metal clustering are negligible. It has been discerned that it is the Kubas interaction which plays the key role in the interaction between Y and H₂ molecules. The outcomes show that ZTC adorned with Y is a capable material for hydrogen storage which will inspire the instrumentalists to fabricate ZTC based fuel cell device.     

Structural evolution and hydrogen storage performance of Mg3LaHn (n = 9–20)

The magnesium-lanthanum-hydrogen systems possess the goodish stability and high hydrogen storage capacity, which make them perspective as commercial Mg-based hydrogen storage materials. The exploration of these intriguing properties evolving from small atomic and molecule cluster to bulk phase are, to our knowledge, the longstanding challenge. Here, we perform a theoretical study on the structural and electronic properties of Mg₃LaH_n (9 ≤ n ≤ 20) clusters by using the Crystal Structure AnaLYsis by Particle Swarm Optimization method combined with density functional theory calculations. It is found that Mg₃LaH₁₅ is the most stable cluster in the series, with hydrogen storage capacity of 6.6 wt% and adsorption energy of 2.76 eV. The present results offer new insights for the design and synthesis of novel hydrogen storage materials in the future.     

Microstructure and hydrogen storage properties of Ti–V–Cr based BCC-type high entropy alloys

In this work, the crystal structure and hydrogen storage properties of V₃₅Ti₃₀Cr₂₅Fe₁₀, V₃₅Ti₃₀Cr₂₅Mn₁₀, V₃₀Ti₃₀Cr₂₅Fe₁₀Nb₅ and V₃₅Ti₃₀Cr₂₅Fe₅Mn₅ BCC-type high entropy alloys have been investigated. It was found that high entropy promotes the formation of BCC phase while large atomic difference (δ) has the opposite effect. Among the four alloys, the V₃₅Ti₃₀Cr₂₅Mn₁₀ alloy shows the highest hydrogen absorption capacity while the V₃₅Ti₃₀Cr₂₆Fe₅Mn₅ alloy exhibits the highest reversible capacity. The cause of the loss of desorption capacity is mainly due to the high stability of the hydrides. The higher room-temperature desorption capacity of the V₃₅Ti₃₀Cr₂₅Fe₅Mn₅ alloy is due to higher hydrogen desorption pressure. After pumping at 400 °C, the hydrides can return to the original BCC structure with only a small expansion in the cell volume.     

Hydrogen storage properties of Mg–Ni–C system hydrogen storage materials prepared by hydriding combustion synthesis and mechanical milling

Mg–Ni–C composite hydrogen storage materials were prepared by first ball milling the powder mixtures of carbon aerogel and nano-Ni, and then mixed with magnesium powder followed by hydriding combustion synthesis (HCS). The HCS product was further treated by mechanical milling for 10 h. The effect of Ni/C ratio on the structures and hydrogen absorption/desorption properties of the materials were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and pressure–composition–temperature (PCT) measurements. It is found that 90Mg–6Ni–4C system shows the best hydriding/dehydriding properties, which absorbs hydrogen at a saturated capacity of 5.23 wt.% within 68 s at 373 K and desorbs 3.74 wt.% hydrogen within 1800 s at 523 K. Moreover, the dehydriding onset temperature of the system is 430 K, which is 45 K lower than that of 90Mg–10Ni system or 95 K lower than that of 90Mg–10C system. The improved hydriding/dehydriding properties are related greatly to the Ni/C ratio and the structures of the composite systems.     

Structural,electronic and thermodynamic properties of Al- and Si-doped α-, γ-, and β-MgH2: Density functional and hybrid density functional calculations

In this work, we present a detailed study of Al- and Si-doped α-, γ-, and β-MgH₂ phases using the gradient corrected density functional GGA-PBE and the hybrid Hartree–Fock density functionals PBE0 and HSE06 within the framework of generalized Kohn–Sham density functional theory (DFT) using a plane-wave basis set. We investigate the structural, electronic, and thermodynamical properties of these compounds with regard to their hydrogen storage effectiveness. PBE0 and HSE06 predict cell parameters and bond lengths that are in good agreement with the GGA-PBE calculations and previously known experimental results. As expected smaller band gaps (E_gs) are predicted by GGA-PBE for the pure magnesium hydride phases. PBE0 overcomes the deficiencies of DFT in treating these materials better than HSE06 and yields E_gs that compare even better with previous GW calculations. Both the hybrid functionals increase the E_gs of the Al-doped magnesium hydrides by much less magnitudes than of the Si-doped phases. This difference is interpreted in terms of charge density distributions. Best H₂ adsorption energies (ΔH_ads) are computed by HSE06 while GGA-PBE significantly overestimates them. Si-doped α- and β-MgH₂ exhibited the least negative ΔH_ads in close proximity to the H₂ binding energy range of −0.21 to −0.41 eV ideal for practical H₂ storage transportation applications.     

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

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

Free-standing CuS–ZnS decorated carbon nanotube films as immobilized photocatalysts for hydrogen production

Free-standing carbon nanotube films (CNTF) with entangled carbon nanotubes (CNT) were used as conductive supports for the preparation of CuS–ZnS/CNTF composite as immobilized photocatalysts for H₂ production. The surface morphology, crystalline property, surface chemistry, and optical properties of the CuS–ZnS/CNTF photocatalysts were investigated. The effects of forming CuS–ZnS heterojunction and conductive CNTF on the separation of photogenerated charges and photocatalytic hydrogen production activity of CuS–ZnS/CNTF photocatalysts were evaluated by the photocatalytic hydrogen production tests. Conductive CNT films can prevent the recombination of photogenerated electron–hole pairs. The deposition of CuS nanoparticles on the ZnS/CNTF leads to higher photocatalytic activity which can be attributed to the effective electron–hole separation. Introducing ZnS and CuS makes the photocatalyst surface more hydrophilic. The porous structure contributed to the effective contact between the sacrificing agents and the photocatalysts, leading to enhanced H₂ production activity.     

The potential of transition metal–methylidynes as high-capacity hydrogen storage media

With respect to density functional predictions, TM–methylidynes (TM = Sc, Ti, V, and Cr) bind high-density hydrogen at ambient conditions. TM–methylidyne complexes can adsorb up to seven hydrogen molecules. The predicted maximal retrievable hydrogen storage density is 16.7 wt% for ScCH, a record high value so far, larger than the 16.0 wt% for TiCH, 13.2 wt% for VCH, and 13.0 wt% for CrCH. Dimerization and oligomerization of scandium–methylidyne lower the hydrogen storage capacity to 9.2 wt% for the dimer and to 7.9 wt% for the hexamer. These predictions provide useful guidance for designing novel hydrogen storage materials with optimal gravimetry and kinetics and for devising possible schemes by which the hydrogen/host material interactions can be manipulated.