CeO2基固溶体对Mg2Ni合金储氢动力学性能的影响研究

采用水热法合成纳米Ce_1-x(Eu_0.5La_0.5)_xO₂及Ce_1-x(Fe_0.5La_0.5)_xO₂固溶体, 通过结构及光谱性能分析表征了掺杂效应。与纯CeO₂--相比, CeO₂基固溶体的晶胞参数变大, 紫外漫反射的吸收边发生移动, 拉曼光谱的F_2g特征振动峰向低波数方向移动。将掺杂固溶体作为添加剂与Mg₂Ni合金混合进行球磨处理, 对得到的复合材料进行结构及储氢动力学表征。XRD结果表明, 复合材料的纳米晶比例升高。储氢动力学测试结果表明, 固溶体添加剂使材料表面反应的可逆程度得到优化, Mg₂Ni合金体内的氢原子扩散速率及氢扩散系数也得到了提高。     

Cu的添加对Mg2Ni合金储氢性能的影响

采用机械合金化法,制备了Mg2Ni1-xCux(x=0、0.1、0. 3)合金,研究了Cu对Mg2Ni储氢合金储氢性能的影响.XRD和SEM研究表明Cu的加入使合金中产生了Cu11Mg10Ni9新相.利用PCT测试仪测定了合金的储氢性能,结果表明,添加Cu元素会降低合金的吸氢量,但能有效地提高放电容量和循环稳定性.制备出的Mg2Ni0.9Cu0.1与Mg2Ni0.7Cu0.3相比,前者具有较大的吸氢量,后者的放电容量较大,循环稳定性较好.     

采用机械合金化方法制备Ti3Ni2合金的结构及电化学储氢性能

采用机械合金化方法用Ni粉和Ti粉得到了Ti3Ni2非晶合金。晶态Ti3Ni2合金初始容量比非晶合金要高。晶态合金初始容量可以达到240mAh／g。而非晶合金容量为173mAh／g。随着循环次数的增加，晶态合金放电容量呈线性下降趋势。而对于非晶电极材料来说，随着循环的进行，初始容量下降，但是达到一定循环次数以后，电极的放电容量达到基本稳定。     

Al的添加对Mg2Ni合金储氢性能的影响

采用两步法(球磨 烧结),制备了Mg2-xAlxNi(x=0、0.1、0.3)合金,研究了Al对Mg2Ni合金储氢性能的影响.XRD和SEM研究表明Al的加入使合金中产生了Mg3AlNi2新相.利用PCT测试仪测定了合金的储氢性能,结果表明:添加Al元素会降低合金的吸氢量,但能有效地提高放电容量和循环稳定性.制备出的Mg1.9Al0.1Ni和Mg1.7Al0.3Ni相比,前者具有较大的吸氢量,后者的放电容量较大,循环稳定性较好.     

机械合金化制备的Mg-Al-Ni系储氢合金及其性能

在机械合金化的过程中不断增加球料比,在24h内制得性能较好的Mg-Al-Ni系储氢材料.用P-C-T曲线测试仪进行测试,并利用X射线衍射和扫描电镜对材料吸放氢前后的变化进行了表征.研究表明,Mg1.8Al0.2Ni合金的吸氢相为Mg2Ni和由Mg、Al、Ni元素组成三元化合物.球磨26h Mg1.8Al0.2Ni粉末试样在150℃下开始吸氢.     

机械合金化法制备镁基储氢合金的研究进展

机械合金化法是制备镁基储氢合金的较佳工艺。对近年来机械合金化法制备镁基储氢合金的研究开发,特别是在多元合金化、复合储氢合金等方面的发展进行了系统阐述。总结认为,机械合金化法可以显著改善镁基储氢合金的动力学性能和电化学性能,提高储氢量。未来镁基储氢合金应向复合材料、新方法与机械合金化法相结合、材料的计算机设计等方面发展。     

镁基复合材料(Mg-Ni-MO)的储氢性能

在充氢气条件下，用机械球磨的方法合成了（RMA）镁基纳米复合材料Mg-3Ni-2MO(质量分数，％）（MO－过渡金属氧化合：Cr2O3,MnO2,V2O5,NiO,ZnO)。研究了材料的吸氢和放氢性能，在吸放氢过程中温度的变化规律，特别是在吸氢过程中产生的引燃现象。研究了材料的组成和球磨时间对吸放氢性能的影响。结果表明，含有过渡金属氧化物的镁基纳米复合物都具有较好的吸放氢动力学性能和较低的放氢温度。     

Mg2Ni纳米晶储氢材料的机械合金化制备工艺研究

利用机械合金化方法制备了Mg2Ni纳米晶粉末,根据不同球磨参数下样品的X射线衍射结果,分析了球磨过程中相组成、粉末晶粒度等的变化,研究了球磨时间、球磨转速、过程控制剂等工艺条件对粉末晶粒度、机械合金化程度的影响.结果表明:在较高的转速下进行循环变速运行并加入合适的过程控制剂可以使生成Mg2Ni的时间提前,完全合金化的过程缩短,得到的Mg2Ni晶粒度为10nm左右.对Mg2Ni纳米晶粉末进行了初步的贮氢性能研究,结果表明:机械合金化制备的样品在室温下即可吸氢,贮氢性能较之传统材料有较大改善.     

机械合金化过程中各种因素对储氢合金结构和性能的影响

机械合金化是最近发展起来的制备储氢材料的新型工艺,在改善材料结构和储氢性能方面显示出非常有效的作用.然而,在机械合金化过程中的各种因素,包括球磨时间、球磨环境、球料比等,对合金的结构和储氢性能有不同程度的影响.综述了国内外在机械合金化方面的研究,为更进一步探索通过调整这些因素来改善储氢合金性能有一定的指导意义.     

球磨La2Mg17与Ni复合合金的电化学贮氢性能研究

利用机械合金化法制备了La2Mg17+200%(质量分数)Ni复合储氢合金,并对不同球磨时间时合金的微观结构和电化学性能进行研究。结果发现,在球磨过程中Ni粉诱导了La-Mg-Ni非晶/纳米晶结构的形成。XRD和HRTEM结果共同表征了球磨80h时,合金中有Ni金属的存在,且XRD衍射峰强度较低,宽化严重,SAD为宽化的多环,表明形成非晶结构。电化学及其反应动力学测试结果发现,不同球磨时间的电化学反应的动力学控制机理是不同的。球磨60和80h后合金中不仅存在La-Mg-Ni非晶相,同时也有催化剂金属Ni,使合金的表面电荷转移反应电阻较小,氢在合金体相内的扩散系数D和极限电流密度I L均最大,最终导致80h的放电容量为最大值948.3mAh/g。然而,当合金的球磨时间为100和120h时,合金粉化到纳米级,100h的电荷转移反应电阻R ct最大,合金表面电化学反应缓慢,且合金体相内的极限电流密度和氢扩散系数均最小,属于合金电解液表面间的电荷转移和氢向体相内扩散联合控制的过程,必然导致其放电比容量较小。     

Formation of magnesium nanocomposite via mechanical milling

Nanocomposite Mg5wt%Al has been synthesized via mechanochemical milling of elemental Mg, Al and Ti powders with polyethylene–glycol. TiH₂ phase was formed through the reaction between Ti and polyethylene–glycol during the milling as well as the sintering processes. Formation of ultra-fine particles of a few nanometer in size was observed within the matrix grains. The formation of TiH₂ particles is hypothesized to occur through two stages. In the first stage, Ti is supersaturated in the Mg matrix during high energy milling while polyethylene–glycol decomposes to react with Mg as well as Ti which is not solid solute in the Mg matrix. In the second stage during sintering, the hydrogen and Ti released from the Mg react with each other, thus forming nanoparticles. As a result of the nanoparticles, the nanocomposite manifests improved yield strength and ductility in comparison to it counterpart.     

Effect of mechanical milling and heat treatment on the structure and magnetic properties of gas atomized Mn-Al alloy powders

Ferromagnetic Mn-Al alloy powders were fabricated by mechanical milling and heat treatment with gas-atomized powders. Different processes, i.e., heat treatment before ball milling and ball milling before heat treatment, result in different microstructures and magnetic properties of the powders. It was found that H_c increased and M_r decreased with the size reduction regardless of the sequence of heat treatment and ball milling. However, tendency of the change in H_c and M_r depended on the sequence. Further annealing of the powders ball-milled after heat treatment resulted in slight decrease of H_c and large increase of M_r. The magnetic properties, M_r = 41.2 emu/g, H_c = 3.1 kOe, were obtained from the powders ball-milled for 5 h after heat treatment at 650 °C for 20 min, and subsequent annealing at 280 °C for 20 min.     

La1.5Mg0.5Ni7-xCux(x=0.1～1.2)贮氢合金电化学性能的研究

研究了Ce2Ni7型贮氢合金La1.5Mg0.5Ni7-xCux（x=0.1-1.2）的组织结构和电化学性能。当X=0．1—0．6时Cu元素部分替代Ni后可形成La2Ni7型相，x≥0．9时，合金中则有少量的未知相析出。合金MH电极电化学研究表明，随Cu元素量的增加，合金电极的最大放电容量从380mAh／g（x=0．1）下降至340mAh／g（x=1．2）；当x=0．3～0．9时合金电极的循环寿命较x=0．1时有一定的改善，合金电极交换电流密度（I0）和极限电流密度（I1）均以x=0．6为转折点先减小后增大。电极反应的动力学性能依Cu0．1〉Cu0．3〉Cu1．2〉Cu0．9〉Cu0．6的次序递减。     

Characteristics of Hydrogen Storage Alloy Mg2Ni Produced by Hydriding Combustion Synthesis

A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigatedby means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showedthat the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis withoutany activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp(0.1 Mpa)=3026/T 5.814 (523 K≤ T ≤623 K) for hydriding and Igp (0.1 Mpa)=-3613/T 6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1 - α)]3/2 = kt and the apparent activation energy for thenucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31 kJ/(mol.H2)and 59.9±2.99 kJ/(moI.H2) respectively.     

Overview of processing of nanocrystalline hydrogen storage intermetallics by mechanical alloying/milling

The objective of this article is to overview processes of mechanical alloying/milling (MA/MM), and their modifications applied to produce nanostructured single- and multi-phase intermetallics, and their composites, for hydrogen storage. In the most typical processing, MA is used as a preliminary step in synthesizing a nanostructured intermetallic powder starting from elemental metal powders. In a subsequent step, the intermetallic powder is hydrogenised under high pressure of hydrogen to produce nanostructured intermetallic hydride. A modified processing variant combines the synthesis of nanostructured intermetallic and its subsequent hydrogenising in one step by MA of elemental metal powders directly under hydrogen atmosphere to form nanostructured intermetallic hydrides (so-called Reactive Mechanical Alloying—RMA). The MM can be applied to produce nanostructured intermetallic powders from pre-alloyed intermetallic cast ingots or to manufacture nanocomposites, by mixing with dissimilar material before milling, which could be hydrogenised in a separate process. In addition, pre-alloyed bulk intermetallics can be mechanically milled directly under hydrogen atmosphere (Reactive Mechanical Milling—RMM) in order to obtain nanostructured intermetallic hydrides as a final product. All the above processes are critically discussed in the present article. The effect of nanostructurization on the hydrogen sorption/desorption characteristics of intermetallics and/or their hydrides is also discussed.     

Hydrogen absorption/desorption properties of Li–Al–N–H composite

Li₃AlH₆ and LiNH₂ at a 1:3 molar ratio were mechanically milled to yield a Li–Al–N–H composite. The hydrogen storage properties of the composite were studied using thermogravimetry, differential scanning calorimetry, mass spectrometry, and X-ray diffraction. Addition of LiNH₂ lowered the decomposition temperature of Li₃AlH₆. The Li–Al–N–H composite began to release hydrogen at around 110 °C, which was 90 °C lower than the initial desorption temperature of Li₃AlH₆. About 7.46 wt% of hydrogen was released from the composite after heating from room temperature to 500 °C. A total hydrogen desorption capacity of 8.15 wt% was obtained after accounting for hydrogen released in the ball-milling process. The resulting dehydrogenated composite absorbed 3.56 wt% of hydrogen at 400 °C under a hydrogen pressure of 110 bar. The hydrogen absorption capacity and kinetic properties of the Li–Al–N–H composite significantly improved when CeF₃ was added to the composite. A maximum hydrogen absorption capacity of 4.8 wt% was reached when the composite was doped with 2 mol% CeF₃.     

Mg Amorphous Zr0.9Ti0.1（Ni0.57Mn0.28V0.1Co0.05）2.1 Composite for Hydrogen Storage

The reactive mechanical alloying (RMA) method was used to produce Mg-40 wt pct amorphous Zr0.9Ti0.1(Ni0.57-Mn0.28V0.1Co0.05)2.l composite in this study, and the absorption/desorption property of the composite was improved remarkably. The composite possessed excellent kinetic properties even at moderate temperature (393 K) without activation. Owing to the formation of the embrittle MgH2, the reactive mechanical milling process reduced the particle size of Mg and made the composite phase being highly efficiently distributed, which determined the excellent hydriding properties of the composite.     

球磨时间对镁碳复合储氢材料结构和性能的影响

采用氢气气氛中高能球磨反应法,制备了40Mg60C镁碳复合储氢材料,研究了球磨时间对材料粒度、晶体结构和放氢性能的影响.结果表明,球磨2h材料的粒度即可达纳米级,约10～20nm,球磨时间再延长,材料团聚程度加重;球磨2h的材料为纳米晶和非晶结构,当球磨时间增加到4h时,材料几乎成为非晶结构;球磨时间4h时,材料储氢量已趋于饱和,最大放氢量为3.15%(质量分数);材料放氢温度随球磨时间的增加而降低,球磨5h材料的初始放氢温度和放氢峰温降为275.18和314.94℃.