Superior catalytic effect of TiF3 over TiCl3 in improving the hydrogen sorption kinetics of MgH2: Catalytic role of fluorine anion

TiF₃ shows a superior catalytic effect over TiCl₃ in improving the hydrogen sorption kinetics of MgH₂. Combined phase analysis and microstructure characterization suggest that both titanium halide additives react with host MgH₂ in a similar way. However, systematic X-ray photoelectron spectroscopy studies reveal that the incorporated fluorine (F) differs significantly from its analog chlorine (Cl) in terms of bonding state. The asymmetry of F 1s spectra and the sputtering-induced peak shift suggest that, in addition to the Mg–F bond, a new Ti–F–Mg bonding is formed in the TiF₃-doped MgH₂. In contrast, only one stable binding state of Cl is identified in the form of MgCl₂ for the TiCl₃-doped MgH₂. In combination with the designed experiments, these findings suggest that the generation of active F-containing species may be responsible for the advantage of TiF₃ over TiCl₃ in improving both the absorption and desorption kinetics of MgH₂. Fundamentally, it emphasizes the functionality of F anion in tuning the activity of compound catalyst.     

TEM analysis of the microstructure in TiF3-catalyzed and pure MgH2 during the hydrogen storage cycling

We utilized transmission electron microscopy (TEM) analysis, with a cryogenically cooled sample stage, to detail the microstructure of partially transformed pure and titanium fluoride-catalyzed magnesium hydride powder during hydrogenation cycling. The TiF₃-catalyzed MgH₂ powder demonstrated excellent hydrogen storage kinetics at various temperatures, whereas the uncatalyzed MgH₂ showed significant degradation in both kinetics and capacity. TEM analysis on the partially hydrogen absorbed and partially desorbed pure Mg(MgH₂) revealed a large fraction of particles that were either not transformed at all or were completely transformed. On the other hand, in the MgH₂+TiF₃ system it was much easier to identify regions with both the hydride and the metal phase coexisting in the same particle. This enabled us to establish the metal hydride orientation relationship (OR) during hydrogen absorption. The OR was determined to be (1 1 0)MgH₂ || (?1 1 0 ?1)Mg and [?1 1 1]MgH₂ || [0 1 ?1 1]Mg. During absorption the number density of the hydride nuclei does not show a dramatic increase due the presence of TiF₃. Conversely, during desorption the TiF₃ catalyst substantially increases the number of the newly formed Mg crystallites, which display a strong texture correlation with respect to the parent MgH₂ phase. Titanium fluoride also promotes extensive twinning in the hydride phase.     

Improvement in hydrogen sorption kinetics of MgH2 with Nb hydride catalyst

Nanocrystalline MgH₂ with fine and evenly dispersed Nb hydride was prepared by ball milling a mixture of MgH₂ and 1 mol.% NbF₅. This NbH-catalyzed MgH₂ desorbed 6.3 wt.% H₂ in 15 min and absorbed more than 90% of its initial hydrogen capacity within 5 min at 573 K. Moreover, this fast sorption kinetics was maintained after 10 cycles. Based on X-ray diffraction and transmission electron microscopy/energy-dispersive spectroscopy analyses, it is suggested that NbF₅ melts during high-energy ball milling and this promotes the formation of extremely fine, film-like Nb hydride preferentially along the grain boundaries of nanocrystalline MgH₂ by a liquid/solid reaction. This unique nanostructured Nb hydride is believed to suppress the grain growth of MgH₂ quite effectively and thus maintain its initial catalytic effect throughout repeated hydrogenation–dehydrogenation cycles.     

Cycling hydrogen desorption properties and microstructures of MgH2-AlH3-NbF5 hydrogen storage materials

Magnesium hydride (MgH2) is a candidate material for hydrogen storage.MgH2-AlH3 composite shows superior hydrogen desorption properties than pure MgH2.However,t...     

Ni掺杂MgH2体系解氢性能的机理

采用基于密度泛函理论的Dmol 4.1程序包,通过计算移走H原子所需能量及几何、电子结构的改变,对Ni掺杂MgH2体系解氢性能的机理进行探讨.结果表明:Ni替代Mg和创造Mg空位对MgH2体系解氢而言,均发挥有益作用,而形成Mg空位所需能量(6.51 eV)高于Ni替代Mg所需能量(2.12 eV),表明低温下Ni替代Mg对MgH2体系解氢而言更有利,至此NiF2中的Ni替代MgH2中的Mg,有利于加速化学反应NiF2+3MgH2=MgF2+Mg2NiH4向右进行,使结构稳定的MgH2发生转变,生成结构不稳定的Mg2NiH4,这样体系解氢过程不是通过MgH2,而是转变为通过Mg2NiH4进行,因此,Ni掺杂提高了MgH2体系的解氢性能.     

Co替代Ni改善纳米晶和非晶Mg2Ni型合金的贮氢动力学

为了改善Mg2Ni型合金的贮氢动力学性能,用Co部分替代合金中的Ni,用快淬技术制备了Mg2Ni1？xCox（x=0,0.1,0.2,0.3,0.4）贮氢合金。用XRD、HRTEM表征了快淬态合金的微观结构,用自动控制的Sieverts设备测试了合金的吸放氢动力学性能,用程控电池测试仪测定了合金薄带的电化学贮氢动力学。结果表明：Co替代Ni提高了Mg2Ni型合金的非晶形成能力,合金的非晶化程度随着Co含量的增加而增加。此外,Co替代Ni显著地改善了合金的贮氢动力学,当Co含量从0增加到0.4时,快淬态（15m/s）合金在5min内的吸氢饱和率从81.2%增加到84.9%,20min的放氢率从17.60%增加到64.79%,氢扩散系数从1.07×10-11cm2/s增加到2.79×10？11cm2/s,极限电流密度从46.7mA/g增加到191.7mA/g。     

Hydrogen generation via hydrolysis of nanocrystalline MgH2 and MgH2-based composites

Nanocrystalline MgH2 and MgH2-based composites with 25% （mass fraction） of Al, Ca, or CaH2 as an individual additive respectively were prepared by ball milling. The crystallite size and morphology of the as-milled powders were characterized and their hydrolysis behaviours were investigated in comparison with commercial polycrystalline MgH2. The results show that the crystallite size of both MgH2 and MgH2-based composites is reduced to less than 13 nm after milling for 15 h. Due to its enhanced specific surface area and unique nanocrystalline structure, the as-milled MgH2 shows much better hydrolysis kinetics than the commercial polycrystalline MgH2, with the hydrolysed fraction upon hydrolysing for 70 min enhances from 7.5% to about 25%. As compared with the as-milled MgH2, the MgH2-based composites with either Call2 or Ca as an additive present further greatly improved hydrolysis kinetics, with the hydrolysed fraction for 80 min achieving about 76% and 62% respectively. However, the addition of Al doesn＇t show any positive effect on the improvement of the hydrolysis kinetics of Mg H2.     

Solid-state hydrogen storage: Storage capacity,thermodynamics, and kinetics

Solid-state reversible hydrogen storage systems hold great promise for onboard applications. The key criteria for a successful solid-state reversible storage material are high storage capacity, suitable thermodynamic properties, and fast hydriding and dehydriding kinetics. The LiNH₂ + LiH system has been utilized as an example system to illustrate these critical issues that are common among other solid-state reversible storage materials. The progress made in thermodynamic destabilization and kinetic enhancements via various approaches are emphasized. The implications of these advancements in the development of future solid-state reversible hydrogen storage materials are discussed.     

Microstructure and remarkably improved hydrogen storage properties of Mg2Ni alloys doped with metal elements of Al,Mn and Ti

Mg₂Ni_0.7M_0.3 (M=Al, Mn and Ti) alloys were prepared by solid phase sintering process. The phases and microstructure of the alloys were systematically characterized by XRD, SEM and STEM. It was found that Mg₃MNi₂ intermetallic compounds formed in Mg₂Ni_0.7M_0.3 alloys and coexisted with Mg and Mg₂Ni, and that radius of M atoms closer to that of Mg atom was more beneficial to the formation of Mg₃MNi₂. The hydrogen storage properties and corrosion resistance of Mg₂Ni_0.7M_0.3 alloys were investigated through Sievert and Tafel methods. Mg₂Ni_0.7M_0.3 alloys exhibited remarkably improved hydrogen absorption and desorption properties. Significantly reduced apparent dehydriding activation energy values of ?46.12, ?59.16 and ?73.15 kJ/mol were achieved for Mg₂Ni_0.7Al_0.3, Mg₂Ni_0.7Mn_0.3 and Mg₂Ni_0.7Ti_0.3 alloys, respectively. The corrosion potential of Mg₂Ni_0.7M_0.3 alloys shifted to the positive position compared with Mg₂Ni alloy, e.g. there was a corrosion potential difference of 0.110 V between Mg₂Ni_0.7Al_0.3 alloy (?0.529 V) and Mg₂Ni (?0.639 V), showing improved anti-corrosion properties by the addition of Al, Mn and Ti.     

A comparative study on the hydriding kinetics of Zr-based AB2 hydrogen storage alloys

Two kinetic models (Jander model and Chou model) are used to investigate the hydrogen absorption kinetic mechanism of Zr-based AB₂ type Laves phase alloys (Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5, Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55). The analysis shows that the rate-controlling step is the diffusion process at high temperatures in the range from 673 K to 923 K with a low hydrogen concentration (solid solution phase). Both models can well describe the experimental data but Chou model is preferred. Chou model is simpler and easier to use for analyzing the experimental results. The activation energies calculated using Chou model with the least square method are 29.3 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5, 43.8 kJ/mol H₂ for Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and 48.5 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55, which are close to the values reported in the literature (28.3 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5 and 40.3 ± 1.5 kJ/mol H₂ for both Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55).     

Enhancing hydrogen sorption in MgH2 by controlling particle size and contact of Ni catalysts

A comparative study based on MgH2 ball-milled with altered Ni particle sizes under different conditions was conducted to reveal the effect of close contact betw...     

纳米TiO2对Mg2Ni0.75Cr0.25合金储氢动力学性能的改善

采用扩散烧结法制备了Mg2Ni0.75Cr0.25合金,然后与纳米TiO2颗粒混合球磨得到纳米复合材料.X射线衍射分析结果表明,纳米复合材料由Mg2Ni-Ni复相合金和纳米TiO2组成,平均晶粒度为24～35nm.纳米TiO2颗粒对Mg2Ni0.75Cr0.25合金储氢动力学性能的提高具有催化作用,降低了Mg2Ni0.75Cr0.25合金的吸、放氢温度,使纳米复合材料氢化生成焓明显降低.对纳米复合材料的储氢性能测试结果表明:添加1.5%(质量分数)TiO2的纳米复合材料在373K、4Mpa下5min内完成吸氢,并在463K、0.1Mpa下20min内完成放氢,最大放氢量为2.57%.     

Enhancement of Ti-Cr-V BCC alloys on the dehydrogenation kinetics of Li-Mg-N-H hydrogen storage materials

The hydrogen storage properties of a Li-Mg-N-H material doped by a 4 mol.% Ti₃Cr₃V₄ body centre cubic (BCC) alloy hydride and prepared with a ball-milling method were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and Sievert’s technology test. The results show that the Ti₃Cr₃V₄ BCC alloy hydride/Li-Mg-N-H composite has good reversible hydrogen storage properties. The dehydrogenation kinetics of the Li-Mg-N-H system can be greatly improved by doping the Ti₃Cr₃V₄ BCC alloy hydride. The composite desorbed 4.1 wt.% hydrogen in the first 60 min at 473 K under 0.1 MPa pressure, but when without the BCC alloy addition, only 3.0 wt.% hydrogen was desorbed under the same dehydrogenation condition. It can be deduced that the Ti₃Cr₃V₄ BCC alloy uniformly distributed in the Li-Mg-N-H substrate could decrease the activating energy of hydrogen molecules to H atoms and increase H diffusion paths in the composite, enhancing the dehydrogenation kinetics of the Li-Mg-N-H system.     

Design of Zr-based AB_2 type hydrogen storage alloys

1　INTRODUCTIONPresently ,therearetwokindsofhydrogenstor agealloys (AB5andAB2 )usedinnickel metalhy dride (Ni/MH)battery .AB2 typehydrogenstoragealloyhasworseactivationperformanceandlowerini tialcapacitythoughitscapacityishigherandlifeislongerthanAB5alloy .Atthesametime ,AB2 typehydrogenstoragealloyismoreexpensivethanAB5typehydrogenstoragealloy .AlltheaboveaspectsembarrasstheactualapplicationofAB2 typehydrogenstoragealloy .PropertiesofAB2 typehydrogenstor agealloy ,suchascapacity ,…     

Structure and hydrogen storage properties of MgH2 catalysed with La2O3

The catalytic effect of the addition of lanthanum oxide (La₂O₃), in the range 0.5–2.0 mol%, on the hydrogen storage properties of MgH₂ prepared by ball milling has been studied. The addition of La₂O₃ reduces the formation during milling of the metastable orthorhombic γ-MgH₂ phase. The desorption rate of samples with 1 and 2 mol% La₂O₃ comes out to be about 0.010 wt% per second at 573 K under an hydrogen pressure of 0.3 bar, better than for sample with 0.5 mol% La₂O₃. The presence of LaH₃ after hydrogenation/dehydrogenation cycles has been observed in all samples. The sample with 1 mol% of La₂O₃ gives a lower hysteresis factor compared with sample with 2 mol%.     

Photoelectrochemical characteristics of AB5-type hydrogen storage alloy modified with SrTiO3 photocatalyst

Perovskite-type SrTiO3 powders were prepared by using strontium acetate, tetrabutyl titanate and sodium hydroxide via direct hydrolysis-precipitatlon process. AB5-type hydrogen storage alloy（HSA） electrodes modified with SrTiO3 powders were prepared and the photoelectrochemical characteristics of the as-prepared electrodes were investigated. The results of cyclic voltammograph show that the current of reduction peak increases remarkably under the light irradiation. The obvious photochargeable properties are obtained for the hydrogen storage alloys modified with Perovskite-type SrTiO3 powders. During photocharging process, the potential of the electrode shifts quickly to negative direction and a potential plateau occurs. HSA electrode modified with SrTiO3 powders prepared by direct hydrolysis-precipitation process gives the higher potential of about -0.90 V（vs Hg/HgO） under the light irradiation. SEM observation discloses that a large amount of microcracks occur on the surface of the electrode after photocharging process, which is caused by the formation of hydride in the bulk of electrode.     

Synthesis and characterization of Er doped CaF2 nanoparticles

Er³⁺ doped CaF₂ nanoparticles were synthesized by a chemical co-precipitation method. Effect of the dopant concentrations on the structure and optical properties of the CaF₂ nanoparticles was investigated. The X-ray powder diffraction and transmission electron microscopy analysis was used to characterize the structure and morphology of the nanoparticles. The nanoparticles with different dopant concentration exhibited a sphere-like morphology with diameters of about 8-36 nm. The incorporation of Er³⁺ ions into CaF₂ resulted in the decrease in grain size and deterioration of crystallinity, but enlarged the lattice constants of CaF₂. Additional annealing treatment at 400 °C to the prepared CaF₂ removed the NO₃⁻ and OH⁻ groups adsorbed on the particles’ surfaces, and improved the optical properties of the nanoparticles. The fluorescence intensity, with a maximum at approximately 0.4 mol%, decreased with the increase in doping concentration because of concentration quenching.     

Mg_2Cu基储氢合金的表面复相改性

采用机械球磨法制备Mg2Cu合金,并以该合金为基础,添加质量分数为5%的单质(C、Co、Ni、Cu)或氧化物(Cr2O3、Fe3O4、TiO2、V2O5),通过机械球磨对合金进行表面复相改性。采用p—c—T测试仪测定合金的储氢性能,研究添加不同单质和氧化物对Mg2Cu合金储氢性能的影响。结果表明:在200℃和300℃下,添加C或Fe3O4能够有效提高Mg2Cu合金的活性,使其易与氢气反应,并缩短吸氢时间,增大吸氢量,改善放氢效果;在400℃下,添加Co、Ni、TiO2或Fe3O4能够有效缩短吸氢时间,改善合金的综合储氢性能。     

CrCl_3对球磨Mg-Ni合金储氢性能的影响

以氢气作为保护气 ,用机械合金化的方法 ,将镁粉、镍粉和氯化铬制备成纳米复合物 ,实验证明它具有很好的储氢性能。氯化铬起到了提高吸放氢速度和降低放氢温度的作用。在添加CrCl3 的样品中 ,镁粉末在球磨过程中能完全吸氢 ,而没有添加CrCl3 的试样则很难完全吸氢。用机械合金化制备的Mg96Ni3 (CrCl3 ) 1纳米复合物在 16 0℃和 2MPa氢压条件下 ,在 6 5s内储氢容量达到 6 .0 % ,并能使放氢温度降低到 315℃ ,与不加CrCl3 的样品相比 ,放氢温度降低 15～ 2 0℃。