新型贮氢材料研究的最新动态

"氢经济"概念的引入迫使工业界对贮氢材料的贮氢量提出了高达5～6.5 wt%的新要求.为实现这一目标,自1996年起这一领域的研究重点已从传统的金属氢化物扩展到新型微纳米结构的贮氢材料和络合物贮氢材料.综述其最新动态,着重阐述了以NaAlH4为代表的络合物新型贮氢材料的研究进展.     

活性炭和TiF3共掺杂对NaAlH4放氢-再氢化性能的影响

采用高能球磨法制备了活性炭(AC)和TiF3共掺杂NaAlH4复合储氢材料,研究了TiF3和AC共掺杂NaAlH4后复合材料的吸/放氢性能。结果表明:共掺杂10%(质量分数)AC和3%(摩尔分数)TiF3明显降低了NaAlH4前两步放氢温度,且较单一掺杂而言,共掺杂AC和TiF3更有利于NaAlH4放氢温度的降低;160℃下NaAlH4+TiF3+AC样品在170 min内放氢5.0%(质量分数),完成理论放氢量的93%;4次吸放氢循环后NaAlH4+TiF3+AC依然具有良好的循环稳定性,在160℃、真空下起始放氢以及130℃、9 MPa起始吸氢条件下,NaAlH4可逆储氢量可达4.8%(质量分数)。     

掺杂催化剂对NaAlH4吸放氢性能和微观结构的影响

利用PCT测试仪和X射线衍射及场发射扫描电镜等测试手段对NaAlH4 2%(摩尔分数)M(M=Ni、LaCl3、Ce(SO4)2)的吸放氢性能和微观结构进行了研究.结果表明,催化剂的掺杂均可降低NaAlH4的放氢温度,催化剂的催化效果依次为:Ce(SO4)2＞LaCl3＞Ni.掺杂稀土化合物可改善NaAlH4的吸氢性能,使第一步吸氢反应:3NaH Al (3)/(2)H2Na3AlH6完全发生,特别是Ce(SO4)2的掺杂,使样品发生了部分(1)/(3)Na3AlH6 (2)/(3)Al H2NaAlH4的第二步吸氢反应,吸氢量达到2.808%(质量分数).掺杂Ce(SO4)2有利于NaAlH4 在球磨过程中颗粒尺寸细化,颗粒的细化增强了NaAlH4的活性,导致其吸放氢性能提高.     

金属及金属盐改性NaAlH4的放氢反应研究

采用加入金属及金属盐的方法对NaAlH4进行催化放氢作用的研究.实验证明,加入钼粉、氧化钇、氯化铋,NaAlH4脱氢反应性能明显提高,2％(wt,下同)Mo、2％Y2O3和2％BiCl3的加入对NaAlH4的放氢过程产生了较大的影响,改进了其放氢动力学性能,使NaAlH4的放氢量提高1.0％以上.     

Pd含量对Mg-Ni合金相形成及贮氢性能的影响研究

采用机械合金化方法合成了Mg-54.7%Ni-x%Pd(x=0、3、10,质量百分比)贮氢材料.通过X射线衍射分析(XRD)和贮氢性能测试,研究了Pd含量对Mg-Ni合金相形成及贮氢性能的影响.XRD分析表明,在0.30MPa的氩气气氛下球磨30h后,粉末没有形成合金相;但在523K吸氢时,Mg-54.7%Ni-x%Pd(x=0,3)与氢气反应均生成了大量的Mg2NiH4,而Mg-54.7%Ni-10%Pd的氢化物中大部分为MgH2,只形成了少量的Mg2NiH4.贮氢性能测试结果表明,所制备的材料在473K无需活化即可吸氢;同Mg-54.7%Ni-x%Pd(x=0,10)相比,Mg-54.7%Ni-3%Pd吸放氢速度最快,可逆贮氢容量最大(2.82%,质量百分比).     

熔体快淬对纳米晶和非晶Mg20Ni10-xCox(x≈0～4)合金电化学贮氢性能的影响

为了改善Mg2Ni型合金的电化学贮氢性能,用Co部分替代合金中的Ni.用快淬工艺制备了纳米晶和非晶Mg20Ni10-xCox(x=0、1、2、3、4)贮氢合金,分析了铸态及快淬态合金的微观结构,测试了合金的电化学贮氢性能.研究了Co替代Ni及快淬工艺对合金电化学贮氢性能的影响.结果表明,Co替代Ni不改变合金的Mg2Ni主相,但形成了第二相MgCo2.在快淬(x=0)合金中没有发现非晶相,但快淬(x=4)合金显示了纳米晶、非晶结构,表明Co替代Ni提高了Mg2Ni型舍金的非晶形成能力.熔体快淬显著的改善了合金的电化学贮氢性能,合金放电容量和电化学循环稳定性均随淬速的增加而增加.     

NaAlH4体系中Ti催化剂催化机理研究进展

综述了国内外对于NaAlH4体系中Ti催化剂催化机理的最新研究,阐述了目前学术界存在的对于NaAlH4体系中Ti催化剂作用机理的2种不同观点:取代机理及氧化还原机理.列举了2种机理分别对应的中间产物并进行了分析.对于Ti添加NaAlH4体系的研究提出了一些不足之处以及改进方法.     

稀土系贮氢材料研究现状

论述了稀土系贮氢材料的性能和应用领域,总结了迄今为止开发的稀土系贮氢材料及其主要特点,分析了改善稀土系贮氢材料性能的主要途径,指出了稀土系贮氢材料的发展趋势。     

金属硼化物对LiBH_4的去稳定化作用（英文）

硼氢化锂(LiBH4)因其高达18.4wt%的含氢量而被用于贮氢材料的研究。但LiBH4放氢和再氢化温度较高,因此如何使其去稳定化(destabilization)从而降低其放氢温度成为研究的热点之一。本文报告了金属硼化物MB2(M=Mg,Ti,Zr)和MB6(M=Ca,La)对LiBH4的去稳定化作用。MB2的添加使LiBH4的放氢温度从450℃降低至350℃,而MB6对LiBH4放氢温度的降低作用更大;而且这些金属硼化物还能有效促进LiBH4放氢后的再氢化反应。XRD,FT-IR,DSC和MS等分析结果表明,金属硼化物在LiBH4的首次放氢过程中起着催化剂的作用,并参与随后的再氢化反应。     

纳米贮氢材料及其制备方法的研究进展

贮氢材料纳米化使贮氢材料的发展方向有了一个突破性的飞跃,而纳米贮氢材料的制备是贮氢材料纳米化的基础.详细介绍了纳米贮氢材料的最新研究进展,深入分析和阐述了贮氢合金纳米化提高贮氢性能的机理,综述了各种制备纳米贮氢合金的物理和化学方法,展望了今后纳米贮氢材料制备方法发展的方向和趋势.     

改善LiBH4吸放氢动力学和热力学方法的研究进展

LiBH4有很高的储氢含量,是一种很有应用前途的储氢材料,但是其高吸放氢温度和压力影响了实际应用.综述了近年来LiBH4的研究进展,介绍了目前国内外改进LiBH4吸放氢动力学和热力学的几种主要方法和特点,并展望了其发展前景.     

置氢Ti6Al4V合金的微观组织演变规律

为研究置氢Ti6Al4V合金的高温加工改性机理,从微观组织的角度对合金进行了对比分析.利用OM、SEM、XRD等研究了置氢对Ti6Al4V合金变形前后微观组织演变的影响.研究结果表明:氢的加入不仅使置氢Ti6Al4V合金中β相比例明显增大,而且改变了α相与β相之间的电势差,在氢含量为0.3%~0.5%两相颜色将发生互换,氢含量增加到0.50%以上时,合金中将出现面心立方结构的δ氢化物;随氢含量的增加,合金超塑拉伸变形后的组织由α+β两相等轴晶粒变为粗大的β晶粒,造成α与β界面的协调能力下降,并改变了合金的变形机制.     

NaAlH4空间约束体系的构建及其脱/加氢行为

配位氢化物具有较高的质量储氢密度,已成为国内外储氢材料的研究热点,但尚未解决的脱/加氢温度过高、速率慢和可逆性差等问题是制约其实际应用的主要原因.利用孔性材料的结构特点来构建纳米尺度的空间约束体系,可有效地改善配位氢化物的脱/加氢性能.以NaAlH4为例,介绍了孔性材料的制备和表面修饰,分析了配位氢化物/孔性介质空间约束体系的构建及其且兑/加氢行为.这种空间约束体系为改善配位氢化物的储氢性能提供了一条新途径.进一步构建配位氢化物/孔性介质/催化剂的空间约束体系,实现对配位氢化物的复合催化,将是今后努力的方向.     

Cu合金化Mg2NiH4储氢体系的组织结构与解氢性能

基于机械反应球磨技术在氢气气氛下成功合成了Mg2NiH4及Cu掺杂Mg2NiH4储氢体系,并采用XRD、SEM、DSC及TGA检测手段对其组织结构与解氢性能进行表征。结果显示,适当提高氢压、延长球磨时间均有助于2Mg-Ni混合物氢化反应的完全化及产物结构的纳米化;Cu掺杂可进一步加快混合物的氢化反应速率,但其产物结构的团聚现象却因MgCu2相的出现而趋于严重;综合热分析表明Cu掺杂不仅降低了Mg2NiH4的解氢温度,还加快了体系的解氢速率;研究结果很好地证实Cu元素是改善Mg2NiH4储氢体系解氢性能最理想的合金化元素之一。     

Meso-scale analysis of the creep behavior of hydrogenated Zircaloy-4

During dry storage, creep is the most likely degradation mechanism for spent Zircaloy fuel cladding. The fuel cladding integrity during dry storage depends on the amount of oxidation, irradiation hardening and hydrogen-uptake during in-reactor operation. In this paper, the effect of hydrogen on the creep behavior of Zircaloy-4 cladding material was investigated at different temperatures. Depending on temperature, hydrogen can be found in the sample in solid solution and/or hydride. To capture this phenomenon, a numerical mesoscale model of the hydrogenated material has been built using the Finite Element (FE) Method. The numerical setup explicitly describes the hydrides as an inclusion in a hydrogenated Zircaloy-4 matrix. The matrix creep behavior follows a combined Norton-Bailey and Norton creep rules whereas the hydrides are considered to be elastic material. The creep law was defined in FE Code ABAQUS using the user subroutine CREEP. The comparison of predicted creep behavior obtained from numerical modeling showed good agreement with the results reported in literature. The predicted creep behavior shows a significant effect of hydrides morphology. Particularly, our model is able to seize the competition between the creep strain rate enhancement induced by hydrogen in solid solution and its reduction due to precipitated hydrogen.     

A balance between catalysis and nanoconfinement towards enhanced hydrogen storage performance of NaAlH4

Owing to its favorable thermodynamics and high density,NaAlH4 has been widely regarded as a potential hydrogen storage material,but its practical application is hindered by the sluggish kinetics,high operating temperature and poor cycling stability.Here,taking advantage of Co-doped nanoporous carbon scaffolds as structural host,we develop a new strategy to balance the synergistic effect between the catalytic role of Co nanoparticles and the nanoconfinement role of porous carbon scaffolds via the controllable etching of Co nanoparticles towards enhanced hydrogen storage performance of NaAlH4.The etching of Co nanoparticles creates extra void spaces nearby catalytically active Co nanoparticles,which not only exerts the catalytic effect of Co nanoparticles,but also improves the nanoconfinement role in maintaining the cycling stability towards increased loading ratio and hence high systematic capacity.Induced by this balanced synergistic effect,the peak temperature for the dehydrogenation of NaAlH4 could be reduced to 164 ℃,97 ℃ lower than the bulk counterpart,even under an ultrahigh loading ratio of 67 ％,and more importantly,the reversible systematic hydrogen storage capacity could still reach 3.3 wt.％ after 5 cycles.This work opens up a new avenue to improve the hydrogen storage performance of various complex hydrides.     

Nano-phases of NaBH4 and KBH4

Phase stability and chemical bonding of beta-NaBH4 and beta-KBH4 derived nano-structures and possible low energy surfaces of them from thin film geometry have been investigated using ab initio projected augmented plane wave method. Structural optimizations based on total energy calculations predicted that, for beta-NaBH4 and beta-KBH4 phases, the (011) and (101) surfaces are more stable among the possible low energy surfaces. The predicted critical size of the nano-cluster for beta-NaBH4 and beta-KBH4 is 1.35 and 1.8 nm, respectively. The corresponding critical diameter for the nano-whisker is 2.6 and 2.8 nm respectively for beta-NaBH4 and beta-KBH4. Structural optimization based on total energy calculations show that the bond distances in the surfaces of nano-whisker are found to be higher than that in the bulk material and the calculated H site energies and bond overlap population analysis suggesting that it is considerably easier to remove hydrogen from the surface of the clusters and nano-whiskers than that from the bulk crystals.     

RuFe纳米粒子修饰片状BiVO4协同催化氨硼烷水解产氢

开发高效廉价的催化剂对于清洁能源经济至关重要, 将氨硼烷的催化水解用于氢能源开发前景广阔。本工作首先采用简单回流法制备BiVO₄纳米片, 再通过浸渍还原法制备出Ru/Fe不同摩尔比的RuFe@BiVO₄催化剂, 并在室温下用于催化氨硼烷水解产氢。通过比较载体BiVO₄、Ru@BiVO₄、Fe@BiVO₄、RuFe@BiVO₄以及无载体的RuFe纳米粒子的催化产氢速率发现, 在所有的催化剂中, Ru₁Fe_0.1@BiVO₄具有最高的催化活性, 非贵金属Fe能显著增强Ru的催化性能, 这与RuFe之间强的电子效应以及RuFe纳米粒子与载体BiVO₄间的双功能效应密切相关, 其活化能(E_a)为43.7 kJ·mol^-1, 转化频率(TOF)为205.4 mol_H2·mol_Ru·min^-1。     

Atomic and Molecular Hydrogen Impurities in Liquid 4He

The static properties of a single hydrogen atom and an hydrogen molecule in bulk superfluid ⁴ He are studied by means of the diffusion Monte Carlo method. The analysis includes atomic hydrogen, deuterium and tritium, and molecular hydrogen and deuterium. Our results, which show some differences with previous variational calculations, are in agreement with the only available experimental data corresponding to atomic deuterium. In contrast to the unbinding presented by the atomic impurities, the molecular ones do bind with energies higher than the chemical potential of pure ⁴ He.     

THE INFLUENCE OF HYDROGEN ON THE FATIGUE BEHAVIOUR OF THE BETA-TITANIUM ALLOY Ti-3Al-8V-6Cr-4Mo-4Zr

In order to characterize the influence of hydrogen on the mechanical properties of β-titanium alloys, monotonic tensile and strain-controlled fatigue tests were performed on samples of the metastable alloy Ti-3Al-8V-6Cr-4Mo-4Zr in uncharged (0.5 at.% hydrogen) and hydrogen-charged (3-4 at.% hydrogen) conditions. The hydrogen was introduced into the material during the last 8 h of an ageing treatment (28 h at 482°C) from the gas phase, whereas the reference (uncharged) specimens were annealed completely in vacuum. The results of the mechanical tests indicate that hydrogen slightly increases the strength of the alloy in monotonic as well as in cyclic loading. Under tensile loading the fracture strain decreases as a result of hydrogen. Under cyclic loading both charged and uncharged conditions show initial softening followed by a saturation state. The cyclic lifetime at a constant total strain amplitude, however, is not reduced by the hydrogen charging. The effect of hydrogen on the mechanical behaviour can be interpreted and understood on the basis of microstructural observations that reveal a hydrogen-induced change in the precipitation state. This indirect influence of hydrogen on the microstructure, which leads to a reduction of the mean size of the α-precipitates, in combination with a slight decrease on the volume fraction of the α-phase, seems to dominate over any direct intrinsic hydrogen effect