Si元素对Ti基储氢合金电化学性能的影响

为了改善Ti基储氢合金的电化学性能，采用Si元素部分替代Mn元素的方法，分析研究了Ti基储氢合金Ti03Zr0．225V0.25Mn0．25-xNi0.5Six的相结构及电化学性能。结果表明，合金均由六方结构的C14型Laves主相和立方结构的TiNi第二相构成；随着Si元素替代量x的增大，合金的活化性能降低，而循环稳定性得到很大程度的改善。     

化学计量比对AB5型贮氢合金相结构及电化学性能的影响

对低钴稀土系贮氢合金Ml(Ni0.78Co0.08Al0.06Mn0.08)x(4.8≤x≤5.4)的相结构及电化学性能进行了研究.结果表明在4.8≤x≤5.2的合金中除CaCu5型结构的主相之外,还出现LaNi3第二相,而且合金中第二相(LaNi3)的析出量随着x值的增大而减少,化学计量比x=5.4的合金则有富镍相析出,B侧合金化使低钴贮氢合金形成单相AB5型合金的化学计量比由x=5.0增大至5.2～5.4之间.四种不同化学计量比合金的活化性能都较好,合金的最大放电容量随化学计量比x的增大而增加,过化学计量比(x=5.4)合金具有最大的放电容量,最优的放电电压特性及最佳的循环稳定性,且其高倍率放电性能也较好.     

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…     

Development of Strip Casting Technology in Rare Earth Permanent Magnet Alloys and Hydrogen Storage Alloys in China

The SC technique is now being applied widely in material preparation, especially in rare earth functional materials in virtue of its advanced process and high performance product. The applications of SC technique in rare earth permanent magnet alloys and hydrogen storage alloys were analyzed integrative, on the basis of summary of SC technique development in this paper. The paper mainly includes development history of SC technology, effect of SC technology on alloy microstructure, application of SC technology in RE storage hydrogen alloy and sintered Nd-Fe-B alloy, development of SC equipment and SC product industry. At the same time, the paper points out the existing problem of SC products.     

镍氢电池用贮氢合金多元化降钴的研究

 为了降低贮氢合金中的钴含量，从而降低镍氢电池的价格，在贮氢合金MlNi355Co075Mn04Al03的基础上，依次添加铜、铬、锌及铁元素，得到稀土基多元贮氢合金，并测试和分析了它们的放电容量、循环稳定性以及微观结构。结果表明，采用适量的铜、铬、锌及铁替代钴所得到的低钴贮氢合金仍具有较高的放电容量和较好的循环稳定性，而且其相结构并未改变。     

Effect of Annealing on Rare Earth Based Hydrogen Storage Alloys

Rare earth-based hydrogen storage alloy used as negative electrode materials for nickel-metal hydride (Ni-MH) batteries are used commercially.The effect of annealing treatment with different annealing temperature and time on the MLNi3.68 Co0.78 Mn0.35 Al0.27 and MMNi3.55 Co0.75 Mn0.40 Al0.30 alloys were investigated.The crystal microstructure,pressure-composition-isotherms (p-C-T) and electrochemical properties of alloys were examined by X-ray diffraction (XRD), automatic PCI monitoring system and electrical performance testing instruments.The optimum annealing treatment conditions of two kinds of alloys were determined.     

RE-Mg-Ni系储氢合金高倍率放电性能研究现状

RE-Mg-Ni系储氢合金具有超晶格结构,其主相晶格单元是由一定比率的AB5单元和AB2单元沿c轴交替层叠排列而成。该类型合金自问世以来便以其高容量、易活化的优势受到人们的广泛关注,然而其循环稳定性及高倍率放电性能不尽人意。人们通过大量研究有效提高了其循环稳定性,使其基本满足了商业化要求。但是要将基于该负极材料的镍氢电池应用在混合动力汽车上,仍需改进其高倍率放电性能。系统分析了元素替代、多元合金化、制备工艺、化合物复合、表面处理等手段对RE-Mg-Ni系储氢合金晶体结构及高倍率放电性能的影响。其中元素替代是一种重要且有效的手段,文中分析了不同稀土元素及B侧元素的作用机制,结果表明,B侧组分采用Ni,Co,Mn,Al的储氢合金具有较好的性能。多元合金化是一种复杂的过程,不同元素间可能存在一定的协同作用,研究其作用机制也是下一步的工作重点。通过优化实验方案,综合使用多种改性手段,可以得到高倍率放电性能良好的RE-Mg-Ni系储氢合金,使其基本满足电动工具用镍氢电池的要求,并可望在以后的研究中进一步提高其高倍率放电性能,使其满足混合动力汽车用镍氢电池的要求,实现良好的经济和社会效益。     

Study on Nanocrystalline Rare Earth Mg-Based System Hydrogen Storage Alloys with AB3-Type

A sort of rare earth Mg-based system hydrogen storage alloys with AB3-type was prepared by double-roller rapid quenching method. The alloys were nanocrystalline multi-phase structures composed of LaNi3 phase and LaNi5 phase by X-ray diffraction and scanning electron microscopy analyses, and the suitable absorption/desorption plateau was revealed by the measurement of P-C-I curve. Electrochemical studies indicate that the alloys exhibit good electrochemical properties such as high capacity and stable cycle life, and the discharge capacity is 369 mAh·g-1 at 0.2 C (72 mA·g-1), after 460 cycles, the capacity decay was only 19.4% at 2 C (720 mA·g-1).     

Hydrogen Absorption Thermodynamic Properties of Rare-Earth Based Hydrogen Storage Alloy in Benzene

Ｔｈｅｐｒｏｐｅｒｔｙｔｈａｔｔｈｅｒａｒｅｅａｒｔｈｂａｓｅｄｈｙ ｄｒｏｇｅｎｓｔｏｒａｇｅａｌｌｏｙｓｃａｎａｂｓｏｒｂ/ｄｅｓｏｒｂａｌａｒｇｅａｍｏｕｎｔｏｆｈｙｄｒｏｇｅｎａｔｒｏｏｍｔｅｍｐｅｒａｔｕｒｅｈａｓｂｅｅｎｕｓｅｄｓｕｃｃｅｓｓｆｕｌｌｙｆｏｒｈｙｄｒｏｇｅｎｓｅｐａｒａ ｔｉｏｎ ,ｐｕｒｉｆｉｃａｔｉｏｎ ,ａｎｄｔｒａｎｓｐｏｒｔａｔｉｏｎ .Ｉｎｔｈｅａｐｐｌｉｃａｔｉｏｎｓ ,ｉｎｏｒｄｅｒｔｏａｖｏｉｄｐｒｏｂｌｅｍｓｓｕｃｈａｓｔｈｅｏｂｓｔｒｕｃｔｉｏｎｔｏｇａｓ…     

Effect of Heat-Treatment Process on Properties of Rare Earth Mg-Based System Hydrogen Storage Alloys with AB3-Type

The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed. The electrochemical properties such as cycling stability, activation property, and the plateau voltage of the alloy which was heat-treated in various temperatures and times had different changes during the cycle process, the optimum heat-treatment conditions of this alloy were determined by this work.     

Study on High Rate Discharge Performance and Mechanism of AB5 Type Hydrogen Storage Alloys

The effects of surface treatment, particle size distribution, rare earth composition and B additive on the high rate discharge performance of hydrogen storage alloys were investigated. It is found that the activity, discharge capacity and high rate dischargeability of the alloys are improved after physical and chemical modification as a result of the increase of the surface area and formation of the electrocatalysis layers, which increase both the electrochemical reaction rate on the alloy surface and H diffusion rate in the alloy bulk. It is also found that both the over-coarse and over-fine particle size increase the contact resistance of the electrode, resulting in a decrease of discharge capacity, deterioration of high rate dischargeability and lower discharge plateau. In another word, a suitable particle size distribution can enhance the alloy activity, discharge capacity and high rate dischargeability. In addition, the high rate dischargeability is enhanced by in-creasing La content and decreasing Ce content of the alloy composition because of enlargement of the unit cell volume and the improvement of the surface activity. Moreover, B additive resultes in the formation of the second phase, and makes the alloys easier pulverization, which greatly improves the activity, discharge capacity and high rate dischargeability.     

多元化降钴对贮氢合金性能的影响

为了降低贮氢合金中的钴含量，从而降低镍氢电池的价格，在贮氢合金M1Ni3．55Co0．75Al0．3Mn0．4的基础上，依次添加Cu、Cr、Zn、Fe元素，得到稀土基多元贮氢合金，并对其放电容量和循环稳定性进行了测试和分析。结果表明，适量的Cu、Cr、Zn、Fe替代Co，仍能使贮氢合金具有较高的放电容量和较好的循环稳定性。     

Structure and Electrochemical Properties of A2B7-Type La-Mg-Ni Hydrogen Storage Alloys

~~Structure and Electrochemical Properties of A_2B_7-Type La-Mg-Ni Hydrogen Storage Alloys     

稀土在铜及铜基合金中的作用

稀土作为一种重要的工业原料在铜和铜合金中有着重要的价值，稀土在铜及铜基合金中能起脱气除杂的作用。能改善铜及铜基合金显微结构，提高其强度和硬度及增强热稳定性，还能增强铜合金的耐腐蚀和耐磨性能。     

合金化对Ti-Cr基储氢合金性能的影响

由Ti-Cr基合金的二元相图出发，综述了Ti-Cr基合金的储氢性能，并重点介绍了多元合金化对其储氢性能的影响。合金TiCr1.8中存在BCC和Laves相，吸氢量随温度的升高而有所下降。Zr取代合金中的部分Ti使合金的晶胞参数增大，同时合金的吸氢量增加，平台压力降低，平台区变短。V取代合金中的部分Cr也使合金的吸氢量增加，吸放氢过程中的滞后效应增加。Fe，Mn，Cu，Ni对合金的性能也有一定影响。相同的退火时间下，TiCrV合金的吸氢量随退火温度的升高而增加。     

CO毒化AB5型合金分形特征研究

研究了三种贮氢合金 L a Ni5、L a Ni4 .7Al0 .3、Ml Ni4 .5Al0 .5被 10 0× 10 - 6 CO毒化后的分形特征 ,求出这三种合金在含 10 0× 10 - 6 CO的氢中循环 ,分维分别为 0 .2 5 4 7、0 .170 9、0 .0 72 5。可以较好的解释合金被毒化的宏观现象。     

La0.65RE0.10Mg0.25Ni3.5Si0.15(RE=La,Ce,Pr,Nd,Sm)储氢合金的电化学性能及EIS分析

通过感应熔炼制备La0.65RE0.10Mg0.25Ni3.55i0.15(RE =La,Ce,Pr,Nd,Sm)合金.采用X射线衍射方法分析了合金的相结构,研究了其电化学性能,并采用电化学阻抗谱分析了合金电极的放氢动力学特性.研究结果表明,合金是以LaNi5、LaNi3为主相的多相结构,同时合金中少量的Si元素与Mg和Ni元素形成了少量的Mg2 Si相和Ni2Si相.Ce,Pr,Nd,Sm部分替代La以后,合金的放电容量下降,Ce的替代使合金容量大幅度降低.对于本系列合金,La被其他稀土元素部分替代后,合金经过100次循环后的容量保持率略有下降,但除了Pr元素以外,变化值均较小.合金电极的电化学阻抗谱分析表明,中低频区的容抗弧半径依次为Ce ＞La＞ Nd ＞Sm ＞Pr,这表明采用Nd、Sm、Pr替代La后合金电极在碱液中放电过程电荷传递电阻Rct减小,即合金表面活性增加,但Ce替代却导致Ret急剧增大,这可能与Ce在碱液中易形成氧化物降低了合金的表面活性有关.     

化学计量比对稀土-镁基合金结构和性能的影响

文章研究不同化学计或比的稀土-镁基贮氢合金Mn0.9Mg0.1(NiCoMnAl)5x(x=0.75,0.80,0.85,0.90)相的结构和电化学性能.研究表明,Mn0.9Mg0.1(NiCoMnAl)5x合金的主相均由LaNi5相和LaNi3相组成.但当x≤0.80时,合金中还有LaNi2.28相析出.合金电极的最大放电容量和高倍率性能都随着x值的增大先增加后减少,当x=0.80时,都达到最大值;合金电极在243 K时的放电容量随着x值的增加有显著提高;合金电极的循环稳定性随着x值增大而提高.     

稀土对Al-Mg-Si系合金结构和性能的影响

本文用ＸＲＤ和ＳＥＭ方法研究了稀土对Ａｌ－Ｍｇ－Ｓｉ系合金微观结构的影响，同时还测定了这些合金的耐腐蚀及力学性能。结果表明，该体系的稀土铝合金中大约含０．１０％稀土就可以细化组织，提高使用性能。具有很好的应用前景。     

LaMg11Zr+200%Ni+x%La(x=O,5,10)储氢合金结构及电化学性能

采用机械合金化法(MA)制备了非晶态LaMg11Zr+200%(质量分数,下同)Ni+x%La(x=0,5,10)系列储氢合金,并详细研究了La添加对该系列合金的相结构及电化学性能的影响.结构分析表明,球磨20h该系列合金都呈非晶态,La添加后合金颗粒得到明显细化;电化学研究表明,La添加后,合金电极充电阻力减小,放电容量随La含量的增加而增大,适量v的添加一定程度上改善了合金电极的循环稳定性和动力学性能,LaMg11Zr+200%Ni+5%La合金电极达到最大放电容量597.2mAh·g-1,循环30次后的容量保持率仍为53.5%.