AB5型含Mn储氢合金的研究综述

文章评述了近年来人们对提高AB5型含Mn储氢合金综合性能所进行的研究。通过综述AB5型含Mn稀土系储氢合金Mn在合金中的作用及Mn含量变化、显微结构等对储氢合金的影响,得出储氢合金中Mn对吸氢平台压力、储氢容量、吸放氢速率、循环寿命的影响。通过利用Mn元素对B侧元素的部分或全部替代或Mn被其它元素替代,可以对AB5型储氢合金进行更深入研究,从而进一步提高其综合性能。     

元素替代在AB5型储氢合金中应用的研究进展

简要回顾了AB5型储氢合金的发展历程,综述了元素替代对AB5型储氢合金相结构与储氢性能的影响,总结了各种元素进行替代的研究进展。就目前的研究现状指出了元素替代在AB5型储氢合金应用中存在的问题以及今后的发展方向。     

LaNi_(5-x)Al_x贮氢合金的研究

本研究用Ａｌ置换ＬａＮｉ５合金中的部分Ｎｉ，得到一系列ＬａＮｉ５－ｘＡｌｘ（ｘ＝０．１，０．３，０．５）贮氢合金。对这些合金的吸放氢热力学和动力学性能的实验研究表明，随着Ａｌ的加入及Ａｌ含量的增加，贮氢合金的平台氢压降低，吸氢量有所减少，而吸放氢速度有所增加。通过对合金及其氢化物晶体结构的ＸＲＤ分析，发现Ａｌ的加入并未使晶体结构类型发生变化，只是晶格常数变大；ＬａＮｉ５－ｘＡｌｘ合金吸氢后原晶体结构也未发生变化，但其晶格常数增加较大。     

Phase evolution,hydrogen storage thermodynamics and kinetics of ternary Mg_(90)Ce_5Sm_5 alloy

Greatly stable thermodynamics and sluggish kinetics impede the practical application of Mg-based hydrogen storage alloys.The modifications of composition and structure are important strategies in turning these hydrogen storage properties.In this study,Mg-based Mg_(90)Ce_5 Sm_5 ternary alloy fabricated by vacuum induction melting was investigated to explore the performance and the reaction mechanism as hydrogen storage material by X-ray diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM) and pressure-composition isotherms(PCI) measurements.The results indicate that the Mg-based Mg_(90)Ce_5 Sm_5 ternary alloy consists of two solid solution phases,including the major phases(Ce,Sm)5 Mg_(41) and the minor phases(Ce,Sm)Mg_(12).After hydrogen absorption,these phases transform into the MgH2 and(Ce,Sm)H_(2.73) phase,while after hydrogen desorption,the MgH2 transforms into the Mg phase,but the(Ce,Sm)H2.73 phases are not changed.The alloy has a reversible hydrogen capacity of about 5.5 wt% H_2 and exhibits well isothermal hydrogen absorption kinetics.Activation energy of 106 kJ/mol was obtained from the hydrogen desorption data between 573 and 633 K,which also exhibits the enhanced kinetics compared with the pure MgH2 sample,as a result of bimetallic synergy catalysis function of(Ce,Sm)H_(2.73) phases.The rate of hydrogen desorption is controlled by the release and recombination of H_2 from the Mg surface.Furthermore,the changes of enthalpy and entropy of hydrogen absorption/desorption were calculated to be-80.0 kJ/mol H_2,-137.5 J/K/mol H_2 and 81.2 kJ/mol H_2,139.2 J/K/mol H_2,respectively.     

稀土-镍系贮氢合金研究与开发现状

稀土-镍系贮氢合金是一类重要的贮氢合金。作为贮氢介质具有贮氢量大、价格便宜及抗中毒等优点。本文详细综述了稀土-镍贮氢合金的氢化性能、改性处理及研究现状。     

高频燃烧红外吸收法测定稀土系贮氢合金中碳

以铁、钨、锡为助熔剂,建立了高频红外吸收法测定稀土系贮氢合金中碳含量的新方法。实验表明:分析电流为165~175 mA,经灼烧后坩埚内部表面较光滑,结果的相对标准偏差(RSD,n=5)均小于2%;称样量为0.15~0.30 g时,结果的相对标准偏差(n=5)均小于3%;助熔剂为0.5 g铁-0.9 g钨-0.1 g锡,经灼烧后坩埚内部表面光滑,结果的相对标准偏差(n=6)为1.9%。方法检出限为0.000 225%,方法测定下限为0.000 751%。将实验方法应用于稀土系贮氢合金实际样品的测定,11次测定结果的相对标准偏差在1.9%~3.4%之间。在稀土系贮氢合金实际样品中加入碳酸钡进行碳含量的加标回收试验,回收率在99%~105%之间。
     

V-Ti-Fe储氢合金的真空精炼

采用真空感应炉对金属热还原法制备的V-Ti-Fe合金进行精炼,考察金属铈对精炼效果的影响。结果表明,铈可有效脱除合金中的氧杂质,减少合金内的富钛相和硅偏聚相,降低合金的成分偏析,促进合金的吸氢活化。随铈用量的增加,脱氧效果也逐渐增强,储氢容量得到提升,当铈添加量达到合金用量的5%时,氧含量降到了0.05%,最大吸氢量和有效放氢量分别达到3.36%和1.85%。     

循环伏安法测定纳米晶贮氢合金中氢扩散系数

用双辊快淬法制备了纳米晶稀土贮氢合金,XRD图谱表征为结晶较好的CaCu5六方结构,Scherrer公式计算晶粒大小约为40nm。利用循环伏安法测定了纳米晶稀土贮氢合金电极中的氢扩散系数(DH=1.67×10-7cm2/s),由于纳米晶粒具有较高的结晶度和细小的晶粒尺寸,高密度晶界为氢在合金内部的扩散提供快速通道,提高了贮氢合金的吸放氢效率,从而提高了氢的扩散性能,使电极中氢的扩散系数增大。     

从稀土储氢合金冶炼废渣中回收稀土镍钴合金的研究

对于稀土储氢合金冶炼废渣粉,采用水热酸溶-还原扩散-电弧熔炼的方法回收稀土氧化物和稀土镍钴合金。废渣粉首先用水热酸溶法分离其中的部分稀土氧化物,得到的合金富集物配加金属钙粒用还原扩散法将其中剩余的稀土氧化物转化为AB5型合金,还原扩散得到的合金粉采用电弧熔炼得到稀土镍钴合金。回收的合金杂质含量低,可作为基础原料用于熔炼AB5型稀土储氢合金,实现了稀土储氢合金冶炼废渣的循环利用。     

Low-Temperature Hydrogen Storage Alloy and Its Application in Ni-MH Battery

Rare earth compositions, La, Ce and Pr in Mm(NiCoMnA1)5 hydrogen storage alloy, were arranged by uniform design method. The discharge performances and kinetics parameters including capacity, exchange current density, symmetry factor and hydrogen diffusion coefficient of the alloy at -40℃, were tested in standard tri-electrode cell. And linear regression method was used to analyze the effect of rare earth compositions on the performances of hydrogen storage alloys. The results show that the capacities of the alloys are positively correlative to the square of Ce content at - 40℃ and under both 0.4 and 0.2C rate. The kinetics parameters and hydrogen diffusion coefficient indicate that the low-temperature performances of the alloys are mainly controlled by hydrogen diffusion process, and the surface electrochemical reaction affects the low-temperature performances to a certain extent. The low-temperature discharge capacities of the battery were also tested. The results show excellent low-temperature performances. The battery delivers 69.6% of its room-temperature capacity at -40℃ and 0.2C rate, 77.7% at -40℃ and 0.4C rate, 59.1% at -45℃ and 0.2C rate.     

钒基固溶体型贮氢合金的研究进展

金属钒具有吸氢量大、抗粉化性能好等优点，但是有效吸氢量较低，只有一半的氢能够释放出来，没有实用价值。在V-Ti二元合金的基础上形成的三元合金V-Ti-M(M代表Cr，Mn，Fe，Ni等)具有良好的贮氢性能。Ti／Cr比对V-Ti-Cr合金性能影响很大，Ti/Cr比值为0．75时V-Ti-Cr合金具有最大的贮氢量和有效吸氢量，同时热处理可以有效地提高V-Ti-Cr合金的有效吸氢量，并降低V的使用量。添加Mn的三元合金具有BCC和Laves相双相结构。V-Ti-Fe合金的贮氢量很高，并有希望利用便宜的钒铁做钒源。此外，V基固溶体合金还可以用于镍氢电池负极，如V-Ti-Ni合金具有很高的放电容量，目前需要解决其循环稳定性差和成本高的问题。     

Effect of ball milling on hydrogen storage of Mg3La alloy

Hydrogen storage and microstructure of ball milled Mg3La alloy were investigated by X-ray diffraction and pressure-composition-isotherm measurement. The ball milled Mg3La alloy could absorb hydrogen up to 4wt.% at 300 ℃ for the first time, along with a decomposing course. Following tests showed that the average reversible hydrogen storage capacity was 2.7wt.%. The enthalpy and entropy of dehydrogenation reaction of the decomposed ball milled Mg3La and hydrogen were calculated. XRD patterns indicated the existence of MgH2 and LaH3 in the decomposed hydride and the formation of Mg when hydrogen was desorbed. After the first hydrogenation, all the latter hydrogenation/dehydrogenation reactions could be taken place between Mg and MgH2. The ball milled Mg3La alloy exhibited better hydriding kinetics than that of the as-cast Mg3La alloy at room temperature. The kinetic curve could be well fitted by Avrami-Erofeev equation.     

快淬纳米晶/非晶Mg2-xLaxNi (x=0～0.6)合金的贮氢动力学

为了改善Mg2Ni型合金气态及电化学贮氢动力学性能,用La部分替代合金中的Mg,用快淬技术制备了Mg2-xLaxNi(x=0,0.2,0.4,0.6)合金,用XRD,SEM,HRTEM分析了铸态及快淬态合金的微观结构;用自动控制的Sieverts设备测试了合金的气态贮氢动力学性能,用程控电池测试仪测试了合金的电化学贮氢动力学.结果发现,快淬无La合金具有典型的纳米晶结构,而快淬含La合金显示了以非晶相为主的结构,表明La替代Mg提高Mg2Ni型合金的非晶形成能力.La替代Mg明显地改变Mg2Ni型合金的相组成.当La替代量x=0.4时,合金的主相改变为(La,Mg) Ni3+ LaMg3.合金的气态及电化学吸放氢动力学对La含量及快淬工艺敏感,La替代使合金的吸氢动力学降低,但适量的La替代可以明显改善合金的放氢动力学及高倍率放电能力.适当的快淬处理可以提高合金的气态及电化学贮氢动力学,但获得最佳贮氢动力学的快淬工艺与合金的成分密切相关.     

用HAc-NaAc缓冲溶液对AB_5型储氢合金表面改性的研究

用ＨＡｃ－ＮａＡｃ缓冲溶液对ＡＢ５型储氢合金进行表面改性，通过ＸＲＤ、化学分析和恒电流充放电方法进行比较研究发现：这一方法没有改变合金的主体结构，但改变了合金表面层中的元素组成，这对于储氢合金的初期容量的提高有一定作用。     

Phase Structure and Electrochemical Properties of RE-Mg Based Composite Hydrogen Storage Alloys

Rareearth basedAB5 typealloy ,akindofhy drogenstoragealloyusedasnegativeelectrodemateri alsofthenickel/metalhydride (Ni/MH )secondarybattery ,haseasyinitialactivation ,longcyclelifeandlowcost ,butstillasmalldischargecapacity ,poorhigh ratedischargeability(HRD)andpoorpropertiesatlowtemperature[1,2 ] .Therefore ,howtoincreaseitsdischargecapacityandtoimproveotherelectrochemi calpropertiesismeaningfulbothintheoryandinpracticalapplication .Mg basedhydrogenstorageal loysareremarkablebecauseofitsr…     

镁基贮氢合金的研究进展及其制备

贮氢材料的制备是氢能利用的关键技术.作为新型贮氢材料的镁基贮氢合金,由于其具有超高理论电化学容量的优势而受到全世界瞩目.本文阐述了镁基贮氢合金的电化学性能特点,介绍了国内外研究现状,论述了几种主要制备方法的工艺过程、影响因素、特点及优缺点.     

Initial Activation of Hydrogen-Storage Alloy Electrode by Chemical Modification

Ｔｈｅｍｉｓｃｈｍｅｔａｌ（Ｍｍ）ｈｙｄｒｏｇｅｎｓｔｏｒａｇｅａｌｏｙｓｈａｖｅｓｏｆａｒｂｅｅｎｓｕｃｃｅｓｆｕｌｙｄｅｖｅｌｏｐｅｄａｓａｈｉｇｈｃａｐａｃｉｔｙｎｅｇａｔｉｖｅｅｌｅｃｔｒｏｄｅｍａｔｅｒｉａｌｆｏｒｓｅｃｏｎｄａｒｙｂ...     

Phase structure and hydrogen storage properties of LaMg3.93Ni0.21 alloy

The phase structure and hydrogen storage property of LaMg3.93Ni0.21 alloy were studied.XRD and SEM results exhibited that LaMg3.93Ni0.21 alloy consisted mainly of LaMg3,La2Mg17 and LaMg2Ni phases;after hydriding/dehydriding process,all the three phases transformed,La3H7 phase existed and the actual hydrogen absorption phases were Mg and Mg2Ni phases.Pressure-composition-temperature (P-C-T)measurement showed that the reversible hydrogen storage capacity of LaMg3.93Ni0.21 alloy was 2.63 wt.%,and the absorption time for reaching 90%of the storage capacity was 124 s at 523 K,and it was 1850 s for deabsorbing 90%of the maximum dehydrogen capacity.The hydriding process of LaMg3.93Ni0.21 alloy followed the nucleation and growth mechanisms.The enthalpy and entropy for hydriding and dehydriding reactions of the Mg phase in LaMg3.93Ni0.21 alloy were calculated to be-66.38±1.10 kJ/mol H2,-100.96±1.96 J/(K·mol)H2 and 68.50±3.87 kJ/mol H2,98.28±5.48 J/(K·mol)H2,respectively.A comparison of these data with those of MgH2(-74.50 kJ/mol H2,-132.30 J/K·mol H2)suggested that the hydride of LaMg3.93Ni0.21 alloy was less stable than MgH2.The existence of La hydride and synergetic effect of multiphase led to higher reversible hydrogen storage capacity and better kinetic property at lower temperature for LaMg3.93Ni0.21 alloy.     

机械合金化法制备镁基储氢材料进展

介绍了近年来机械合金化法在镁基储氢材料制备上的研究进展，讨论了机械合金化制备非晶、纳米晶镁基储氢材料的机制；从合金替代和多元复合的角度对镁基储氢材料的性能进行了论述：机械合金化法可制备出纳米晶、非晶态的镁基储氢材料，无序区和晶界浓度的增加使得氢原子的吸附和扩散更为容易，制备出的材料具有较高的活性和较快的吸放氢速度。低温吸放氢性能的改善尤其显著；最后指出了机械合金化法制备镁基储氢材料需要注意并加以解决的一些问题。     

凝固方式对钒基储氢合金性能的影响

分别采用空冷、水冷和液氮冷却三种凝固方式制备了V_3TiNi_(0.56)Cr_(0.4)钒基储氢合金,并进行了电化学性能和储氢性能的测试与分析。结果表明,凝固方式对合金电化学性能和储氢性能产生明显影响。分别采用空冷、水冷和液氮冷却的合金,充放电循环20次后放电容量分别衰减了84%、73%、38%,室温最大吸氢量分别达到1.467%、1.514%、1.832%。