氧化物直接制备储氢合金LaNi_5新工艺

以La2O3和Ni O为原料,通过压制与烧结制成La2O3-Ni O圆形阴极片,然后采用固体透氧膜法(solid oxygenion membrane,SOM)直接制备LaNi5储氢材料,分析La2O3-Ni O烧结片的物相组成,及Ca Cl2熔盐中的侵蚀反应;结合循环伏安曲线和电解中间产物的组成,分析电解反应机理。结果表明:SOM法电解La2O3-Ni O烧结片直接制备LaNi5是可行的,电解3 h后,La2O3-Ni O电极片呈海绵状,其成分为LaNi5;电解机理为La4Ni3O10在氩气气氛下转变为La2Ni O4,La2Ni O4与Ca Cl2熔盐反应生成La OCl和Ni O,随后Ni O电解还原出的金属Ni与La OCl反应生成LaNi5;电解的电流效率为86.7%,能耗为3.55(k W·h)/kg,电流效率、能耗及产品形貌方面都优于熔盐电解法和合金熔炼法,有良好的应用前景。     

LaNi_(4.5)Mn_(0.5)合金中分量的快速分析方法

稀土系储氢合金的成分分析,国外多用ICP-AES法。本文结合我国实际,继LaNi_5、LaNi_(4.5)Cu、LaNi_(4.5)Sn(0.5)之后,提出了LaNi_(4.5)Mn_(0.5)合金中分量的分析方法,方法终点锐敏、快速而简便、结果可靠。 镧、镍、锰离子皆可与EDTA生成配合物,其稳定常数分别为15.50,18.60,13.90。此外,镧与氟离子生产溶度积很小的沉淀,锰与三乙醇胺生成稳定的配合物。因此,在pH5～6的试液中加入过量的EDTA,用偶氮胂Ⅲ作指示剂,用Pb~(2+)溶液滴定过量     

Gd_5Si_(1.8)Ge_(1.8)Sn_(0.4)合金的高温相变

为认识合金的高温相变,采用热分析技术对Gd5Si1.8Ge1.8Sn0.4合金可能的高温相变进行了定性研究,并利用高温XRD研究了合金在200～400℃之间的相结构。研究结果表明:升温过程中,Gd5Si1.8Ge1.8Sn0.4合金在200～300℃之间发生了由Gd5Si2Ge2-型单斜结构向Gd5Si4-型正交结构的转变。从而为探索材料方便快捷的制备工艺提供技术支持。     

氧化物原料配比对金属热还原法制备V-Ti-Fe合金的影响

以金属热还原法制备了V-Ti-Fe合金,主要考察了原料中V2O5与TiO2质量比R对炉渣初晶温度及合金成分的影响。结果表明,随着R的降低,渣体的初晶温度显著升高,所得合金中Ti含量和Al、O杂质含量也明显增加,Si含量则基本不变。XRD、SEM和EDS分析结果表明,所制备合金均具有钒基固溶体结构。合金中Ti存在一定偏析,部分集中于富钛相内。当R≤0.6时,在合金中检测到了明显的Al-O夹杂相。     

Mg_(10)Al_((7-x))Li_2Ti_x(x=0,1,2,3)合金的制备及储氢性能研究

在氩气保护下,采用机械合金化法制备Mg_(10)Al_((7-x))Li_2Ti_x(x=0,1,2,3)合金,并通过XRD、SEM以及DSC等手段对合金进行表征。结果表明,适量的Ti替代Al可以提高合金的吸氢量、降低合金的初始氢化/脱氢温度和提高合金氢化/脱氢动力学性能。Mg_(10)Al_((7-x))Li_2Ti_x(x=1,2,3)合金样品比Mg10Al7Li2合金的初始氢化温度都降低了62K,而初始脱氢温度则分别降低了77、98和59K。当Ti的替代量为x=2时,合金的综合储氢性能最好。     

稀土系合金的快速分析——LaNi_(4.9)Sn_(0.1)的测定

本文继原有工作提出了在两份相同的合金试液中测定其分量,方法终点锐敏、简便而快速、分析结果较好.镧、镍和锡离子均能与EDTA生成稳定的络合物,而镧和锡还能与氟离子生成溶解度很小的沉淀,苦杏仁酸能掩蔽锡,根据这些特点,在pH5～6的合金试液中加入过量EDTA,用二甲酚橙作指示剂,用Pb~(2+)标准溶液滴定未络合的EDTA,可得到镧、镍和锡的总量,然后加入NaF,使镧和锡以氟化物形式沉淀而释放出相应的EDTA,用     

MmNi5-x(CoAlMn)x/Mg纳米晶复合储氢合金的吸氢性能

研究了机械合金化制备的ＭｍＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ／Ｍｇ纳米晶复合储氢合金的吸氢特性。通过测定不同镁含量的ＭｍＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ／Ｍｇ纳米晶复合储氢合金的吸氢ＰＣＴ曲线,考察了镁含量对其吸氢特性的影响。根据对吸氢速度的测定研究了机械合金化对储氢合金的吸氢动力学特性的影响。机械合金化制备的纳米晶复合储氢合金的活化性能与ＭｍＮｉＭ５－ｘ（ＣｏＡｌＭｎ）ｘ铸态合金相比有较大的提高,不需活化或只需一次活化即可吸氢,吸氢量及吸氢的动力学性能与铸态合金相比也有很大的提高。最后对机械合金化形成的纳米晶吸氢特性进行了分析。     

热处理对La_(0.53)Ce_(0.47)Ni_(3.4)Co_(0.6)Mn_(0.3)Cu_(0.1)合金相结构和储氢性能的影响

采用感应熔炼法制备La_(0.53)Ce_(0.47)Ni_(3.4)Co_(0.6)Mn_(0.3)Cu_(0.1)储氢合金,并在不同温度下进行热处理,通过XRD对其相组成及结构进行表征,并采用双电极模拟电池测试系统对其储氢性能进行测试与分析。结果表明,随着退火温度的升高,合金的相组成未发生变化,但其晶化程度逐渐增高,晶体缺陷和晶格应力逐渐减少。热处理改善了合金的循环稳定性,提高了合金的电化学容量,但恶化了高倍率放电能力。     

ZrFe_(1.95-x)Mn_xV_(0.10)(x=0,0.05,0.10,0.15)合金的储氢性能研究

利用磁悬浮感应熔炼法制备了ZrFe1.95-xMnxV0.10(x=0,0.05,0.10,0.15)高坪台压储氢合金。采用X射线衍射分析(XRD)、扫描电子显微镜(SEM)和Sievert's体积法研究了Mn部分取代Fe对ZrFe1.95V0.10合金的相结构、吸/放氢PCT性能及吸氢动力学性能的影响。XRD结果表明,当x≤0.10时合金均为C15型立方Laves单相结构,且随着Mn含量的增加,晶格常数逐渐增大;当x=0.15时合金中出现C14型六方Laves第二相,晶格常数略有降低;随着Mn取代量的增加,合金的活化性能改善,滞后系数降低,但坪台斜率增大,放氢坪台压由2.27MPa降至1.12 MPa(243 K下),储氢容量先增后减,在243 K下ZrFe1.85Mn0.10V0.10合金具有最大的储氢容量1.69%(n(H)/n(M)=1.13)及最快的吸氢速率t0.9为46 s。     

透氧膜法直接制备LaNi_4Al合金的研究

采用固体透氧膜(SOM)法电解La_2O_3-NiO-Al_2O_3烧结片,直接制备储氢合金LaNi4Al。该工艺用只允许氧离子通过的固体透氧膜隔开阴极和阳极,可采用较高的电解电压(3.8V)以获取更高的电解速率。采用SEM和XRD分析了烧结阴极片形貌、组成以及在熔盐中浸蚀后的变化,通过电解中间产物相组成分析了反应机理。结果表明:SOM法由La_2O_3-NiO-Al_2O_3直接制备LaNi4Al是可行的;La_2O_3-NiO-Al_2O_3阴极片1150℃烧结后的组成为LaAlO_3、NiO;烧结片电解机理为LaAlO_3脱氧生成LaOCl、Al,NiO脱氧反应生成Ni,随后LaOCl、Al、Ni反应生成LaNi4Al;反应的电流效率为92.7%,能耗3.55kW·h/kg。工艺流程短、效率高,有良好的应用前景。     

Microstructures and electrochemical properties of LaNi3.8-xAlx hydrogen storage alloys

The microstructures and electrochemical properties of LaNi3.8-xAlx (x=0.0,0.1,0.2,0.3 and 0.4) alloys were studied systematically. The microstructures were identified by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The main phases were not changed with the substitution of Ni by Al, but minor phases appeared when x=0.4. With Al content increasing, the cell volume increased and the hydrogen storage capacity increased first and then decreased, and the maximum discharge capacity increased from 209.4 mAh/g (x=0.0) to 285.3 mAh/g (x=0.3) and then decreased to 241.3 mAh/g (x=0.4). Meanwhile, the exchange current density (I0) increased and the diffusion coefficient (D) decreased with the addition of Al.     

放电等离子烧结制备储氢合金的应用研究现状

介绍了放电等离子烧结制备储氢合金的可行性,从La-Mg-Ni系、Mg基、Ti-V基合金的微观结构及其吸放氢性能等角度综述了放电等离子烧结在储氢合金中的应用研究进展,并指出储氢合金吸放氢性能的改善原因在于适当温度的放电等离子烧结促进了合金中新相的形成,控制了合金晶粒尺寸。     

粉末粒度对储氢合金电化学性能与气态储氢性能的影响

采用真空中频感应熔炼炉熔炼La_(0.67)Mg_(0.33)Ni_(2.5)Co_(0.5)合金,机械研磨成粉,分级过筛得到一系列不同粒度的合金粉末(平均粒度为10μm、53μm、77μm、119μm、196μm),通过XRD、SEM、激光衍射法等方法系统地研究分析了粉末粒度对储氢合金La_(0.67)Mg_(0.33)Ni_(2.5)Co_(0.5)气态储氢性能和电化学性能的影响。不同粒度合金气态吸放氢循环后都发生了不同程度的粉化,大颗粒以表面剥落的方式产生细粉,小颗粒以体断裂的方式粉化,小颗粒的抗粉化能力更强,电化学循环后,合金粉末粉化造成粉末掉渣形成孔洞。粒度越小,气态储氢孕育期越短,活化时间越短,电化学活化性能越好。随着合金粒度的减小,理论最大放电容量和实际测试的最大放电容量也随之减小,而理论容量发挥值却在增加。随循环次数增加,气态饱和储氢量和电化学放电容量急剧下降,小粒度合金循环寿命略好于大粒度合金粉。     

SOM法金属氧化物制取金属新技术

以MgF2-CaF2为熔盐电解质,利用固体透氧膜(SOM)法直接电解还原Ta2O5和丁TiO2制备了金属钽和钛,分析了制样压力和电解温度对阴极产物形貌的影响以及电流的变化规律.结果表明:SOM法直接制备金属钽和钛的电解速度快,电流密度高,合理的制样压力为250～332 MPa,电解电压为3.2～3.8 V,电解温度在1 373～1 432 K之间.该方法较FFC有诸多优点,用于对我国各类稀有难熔金属矿资源进行开发利用,具有好的发展前景.     

Influence of melt spinning and annealing treatment on structures and hydrogen storage thermodynamic properties of La0.8Pr0.2MgNi3.6Co0.4 alloy

La0.8Pr0.2MgNi3.6Co0.4 alloys were prepared by induction melting,annealing and melt spinning techniques.The influences of annealing treatment and melt spinning on phase structure and hydrogen storage properties were systematically investigated.The results of X-ray diffraction determine that the as-cast and as-spun La0.8Pr0.2MgNi3.6Co0.4 alloys consist of LaMgNi4 and LaNi5 phases,while only LaMgNi4 phase is present in the as-annealed alloy.The scanning electron microscope images illustrate that the grain of the alloy is significantly refined by melt spin ning tech no logy.The gaseous hydrogen storage kinetic and thermodynamic properties were measured by using a Sievert's apparatus at different temperatures.The maximum hydrogen storage capacity of the as-cast,as?spun and as-annealed La0.8Pr0.2MgNi3.6Co0.4 alloy is 1.699,1.637 and 1.535 wt.% at 373 K and 3 MPa,respectively.The annealed alloy has flatter and wider pressure plateaus compared with the as-cast and as-spun alloys,which correspond to the hydrogen absorption and desorption process of LaMgNi4 and corresponding hydride.Furthermore,the enthalpy and entropy changes of LaMgNi4 during hydrogenation at different temperatures were calculated using Van't Hoff methods.     

Microstructures and Electrochemical Properties of Cobalt-Free LaNi4.0Al0.2Fe0.4Cu0.4-x Snx (x = 0 ～ 0.4) Electrode Alloys Prepared by Casting

The microstructure, hydriding performance, and electrochemical properties of LaNi4.0Al0.2Fe0.4Cu0.4- x Snx(x = 0 ～ 0.4) hydrogen storage alloys prepared by casting were investigated using XRD, SEM, pressure-composition isotherms, and electrochemical measurements. Substitution of Sn for Cu leads to the precipitation of LaNiSn phase. With increasing amount of tin substitution, cell volume, plateau pressures, and discharge capacities of the alloys decrease,whereas the cycle life of the alloys improves.     

Effect of annealing treatment on hydrogen storage properties of La-Ti-Mg-Ni-based alloy

The present study dealt with investigations on the effects of annealing on the hydrogen storage properties of La 1.6 Ti 0.4 MgNi 9 alloys.The experimental alloys were prepared by magnetic levitation melting followed by annealing treatment.For La 1.6 Ti 0.4 MgNi 9 alloys,LaNi 5,LaNi 3 and LaMg 2 Ni 9 were the main phases,Ti 2 Ni phase appeared at 900℃.Annealing not only enhanced the maximum and effective hydrogen storage capacity,improved the hydrogen absorption/desorption kinetics,but also increased the discharge capacity.The cyclic stability had been improved markedly by annealing,e.g.,when the discharge capacity reduced to 60% of maximum discharge capacity,the charge/discharge cycles increased from 66(as-cast) to 89(annealed at 800℃) and 127 times(annealed at 900℃).La 1.6 Ti 0.4 MgNi 9 alloy annealed at 900℃ exhibited better electrochemical properties compared to the other two alloy electrodes.     

The mechanism of hydrogen induced cleavage in Fe-3 pct Si alloy

Hydrogen promotes the cleavage fracture of Fe-3 pct Si alloy. Hydrogen atmospheres moving alone with a dislocation will reduce the strain energy of the dislocation, resulting in decreasing the exte nal stress necessary to operate the Frank-Read source. Thus, hydrogen can promote dislocation mul tiplication, which has been verified using a dislocation decoration technique. Fractography and mechanics analysis indicate that a set of the [001] sessile dislocations on the [001] plane is just a cleavage microcrack. Hydrogen carried by the gliding dislocations will enter into the microcrack and the hydrogen pressure will augment the external stress and reduce the critical numbern necessary to form a stable cleavage crack and the numberm of the piled-up dislocations. This indicates that hydrogen promotes the formation of the stable cleavage crack before the other slip systems operate