An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg<Subscript>12</Subscript>-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg₁₂-type LaMg₁₁Ni + x wt% Ni (x = 100, 200) alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter (DSC) connected with a H₂ detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability (HRD) and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.     

Electrochemical Hydrogen Storage Performance of the Nanocrystalline and Amorphous Pr-Mg-Ni-based Alloys Synthesized by Mechanical Milling

The PrMg12-type composite alloy of PrMg₁₁Ni + x wt% Ni (x=100,200) with an amorphous and nanocrystalline microstructure were synthesized through the mechanical milling.Effects of milling duration and Ni content on the microstructures and electrochemical hydrogen storage performances of the ball-milled alloys were methodically studied.The ball-milled alloys obtain the optimum discharge capacities at the first cycle.Increasing Ni content dramatically enhances the electrochemical property of alloys.Milling time varying may obviously impact the electrochemical performance of these alloys.The discharge capacities show a significant upward trend with milling duration prolonging,but milling for a longer time more than 40 h induces a slight decrease in the discharge capacity of the x=200 alloy.As milling duration increases,the cycle stability clearly lowers,while it first declines and then augments under the same condition for the x=200 alloy.The high-rate discharge abilities of the ball-milled alloys show the optimum values with milling time varying.     

球磨参数及Ni比例对Mg2Ni合金储氢性能影响研究

采用中频感应炉熔炼出铸态Mg2 Ni合金,将Mg2Ni合金与一定量的Ni粉进行混合球磨处理.系统研究在不同Ni粉添加量及球磨时间等条件下所得合金样品的结构及储氢性能.研究表明,随着Ni含量的增大及球磨时间的延长,合金的非晶纳米晶结构逐渐增多;合金的最大放电容量及循环稳定性得到明显提升;合金的表面催化活性及合金体相内的H传输能力都有了显著提高.Ni粉的作用主要在于可促进合金非晶化,同时对合金的放氢过程起到了催化的作用.     

Gaseous sorption and electrochemical properties of rare-earth hydrogen storage alloys and their representative applications: A review of recent progress

The improvement of hydrogen storage materials is a key issue for storage and delivery of hydrogen energy before its potential can be realized. As hydrogen storage media, rare-earth hydrogen storage materials have been systematically studied in order to improve storage capacity, kinetics, thermodynamics and electrochemical performance. In this review, we focus on recent research progress of gaseous sorption and electrochemical hydrogen storage properties of rare-earth alloys and highlight their commercial applications including hydrogen storage tanks and nickel metal hydride batteries. Furthermore, development trend and prospective of rare-earth hydrogen storage materials are discussed.     

Gaseous and electrochemical hydrogen storage kinetics of as-quenched nanocrystalline and amorphous Mg2Ni-type alloys

The nanocrystalline and amorphous Mg₂Ni-type Mg₂Ni_1?x Co _x (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo₂ and Mg instead of altering the major phase Mg₂Ni. No amorphous phase is detected in the as-quenched Cofree alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient (D) along with the limiting current density (I _L ) and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.     

Microstructure and Hydrogen Absorption/Desorption Behavior of Mg_(23-x)La_xNi_(10) Alloy

Induction melting was used as a routine method to synthesize Mg_(23)Ni_(10), Mg_(22)LaNi_(10) and Mg_(21)La_2Ni_(10) alloys, and followed by a detailed microstructural characterization which included X-ray diffraction(XRD), scanning electron microscopy(SEM) with energy dispersive spectrometer(EDS), high resolution transmission electron microscope(HRTEM) and hydrogen absorption/desorption measurements. XRD analysis results showed that Mg_2Ni and Mg phases were detected in the XRD pattern of the Mg_(23)Ni_(10) alloy, however, the La addition results in conversion from Mg to LaMg_3 and La_2Mg_(17) phases and appearance of crystal defects included dislocations, twin grain boundary and vacancy in the Mg_(22)LaNi_(10) and Mg_(21)La_2Ni_(10) alloy textures. The total maximum hydrogen absorption capacity was 4.45 wt% for the Mg_(23)Ni_(10) alloy, however, the Mg_(22)LaNi_(10) and Mg_(21)La_2Ni_(10) alloys with vacancy, dislocations and twin grain boundary, absorbed 3.66 wt% and 3.60 wt%, respectively, indicating that the La addition led to decreasing of the maximum hydrogen absorption capacity. Besides, hydrogen absorption/desorption of 90% of saturated state expended for about 456 and 990 s for pristine Mg_(23)Ni_(10) alloy, by contrast, the time decreased owing to improvement of hydrogen absorption and desorption kinetics in the alloy with La element, with which the uptake time for hydrogen content to 90% of saturated state was 150 and 78 s, and 90% hydrogen can be released in 930 and 804 s for Mg_(22)LaNi_(10) and Mg_(21)La_2Ni_(10) alloys in the experimental condition.     

Hydriding and dehydriding kinetics of nanocrystalline and amorphous MgzNi1-xMnx （x=0-0.4） alloys prepared by melt spinning

A partial substitution of Ni by Mn was implemented in order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys.The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xMnx(x=0,0.1,0.2,0.3,0.4) alloys were synthesized by the melt-spinning technique.The structures of the as-cast and spun alloys were studied by X-ray diffractometry(XRD),scanning electron microscopy(SEM) and high resolution transmission electron microscopy(HRTEM).The hydrogen absorption and desorption kinetics of the alloys ...     

Co部分替代Ni对La_(0.4)Er_(0.4)Mg_(0.2)Ni_(3.3-x)Co_xAl_(0.2)(0.1≤x≤0.4)储氢合金结构和电化学性能的影响

为了改善储氢合金La0.4Er0.4Mg0.2Ni3.3-xCoxAl0.2(0.1≤x≤0.4)的结构和综合电化学性能,采用Co部分替代Ni的方法,实验采用高频感应炉制备La0.4Er0.4Mg0.2Ni3.3-xCoxAl0.2(0.1≤x≤0.4)储氢合金。通过X射线衍射技术和电化学测量方法研究储氢合金的晶体结构和电化学性能。XRD图谱显示样品储氢合金主要由LaNi5和La2Ni7相组成,电化学实验表明,随着Co含量的增高,储氢合金电极的最大放电容量和50次循环后的容量保持率S50基本呈现增加状态,放电容量从x=0.1时的225mA·h/g升高到x=0.4时的254.9mA·h/g,容量保持率S50从57.11%(x=0.1)增加到66.10%(x=0.4),但高倍率性能不断下降。通过交流阻抗(EIS)和线性扫描(LS)对Co替代Ni的合金动力学性能分析发现,Co替代Ni后合金的表面电荷转移能力先降低后升高。     

Electrochemical properties and structure of MlNi_(5-x)Sn_x system

The electrochemical properties and structure of M1Ni5-xSnx(x=0-0.5) hydrogen storage alloys were investigated by pressure-composition isotherms, electrochemical measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and atomic parameters. With a small amount of tin substitution, the cycle life increases by 52% (0.5C) and 42% (1.0C), but maximum discharge capacity decreases only by 3.0% and 3.5%, respectively. The cycle life is obviously improved by the low volume expansion and the formed SnO2 surface layers upon electrochemical cycling. The substitution of Ni by Sn leads to an increase of the unit cell volume and charge-discharge cycle life and decrease of the plateau pressure, hysteresis and the hydrogen storage capacity. The standard enthalpy of hydride formation decreases with increasing tin substitution. The main factor that influences the standard enthalpy of the hydriding reaction is the number of the outer orbit electrons and not the atomic size factor.     

硼对稀土系AB5型贮氢合金电化学容量及循环寿命的影响

为了提高低钴AB5型贮氢合金的电化学循环稳定性，在MmNi3．8Co0.4Mn0.6Al0．2贮氢合金中加微量的硼．用真空快淬工艺制备了稀土系低钴AB5型MmNi3．8Co0．4Mn0．6Al0．2Bx(x=0，0．1，0．2，0．3，0．4)贮氢合金，分析测试了铸态及快淬态合金的电化学性能及微观结构，研究了硼对铸态及快淬态合金电化学容量及循环寿命的影响．结果表明，硼使铸态及快淬态MmNi3.8Co0.4Mn0．6Al0．2贮氢合金的电化学容量不同程度地降低，但使电化学循环稳定性大幅度提高．硼对电化学性能的影响主要是促进非晶相的形成．     

Effect of melt spinning on gaseous hydrogen storage characteristics of nanocrystalline and amorphous Nd-added Mg_2Ni-type alloys

Nanocrystalline and amorphous Mg-Nd-Ni-Cu quaternary alloys with a composition of(Mg_(24)Ni_(10)Cu_2)_(100-x)Nd_x(x=0, 5, 10, 15, 20) were prepared by melt spinning technology and their structures as well as gaseous hydrogen storage characteristics were investigated. The XRD, TEM and SEM linked with EDS detections reveal that the as-spun Nd-free alloy holds an entire nanocrystalline structure but a nanocrystalline and amorphous structure for the as-spun Nd-added alloy, implying that the addition of Nd facilitates the glass forming in the Mg_2Ni-type alloy. Furthermore, the degree of amorphization of the as-spun Nd-added alloy and thermal stability of the amorphous structure clearly increase with the spinning rate rising. The melt spinning ameliorates the hydriding and dehydriding kinetics of the alloys dramatically. Specially, the rising of the spinning rate from 0(the as-cast was defined as the spinning rate of 0 m/s) to 40 m/s brings on the hydrogen absorption saturation ratio(R_5~a)(a ratio of the hydrogen absorption quantity in 5 min to the saturated hydrogen absorption capacity) increasing from 36.9% to 91.5% and the hydrogen desorption ratio(R_(1 0)~d)(a ratio of the hydrogen desorption quantity in 10 min to the saturated hydrogen absorption capacity) rising from 16.4% to 47.7% for the(x=10) alloy, respectively.     

A2B7型La0.75Mg0.25Ni3.5-xCrx(x=0～0.3)贮氢合金相结构及电化学性能研究

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xCrx(x=0,0.05,0.1,0.2,0.3)四元贮氢合金,系统地研究了合金B端Cr元素对Ni部分替代对合金相结构及电化学性能的影响.X衍射(XRD)分析表明,La0.75Mg0.25Ni3.5合金是由La2Ni7相组成.随着Cr元素的加入,该类合金中出现LaNi5相及LaNi3相,且随着Cr含量的增加而增多.电化学测试表明,随Cr含量的增加,合金电极活化次数变化不大,最大放电容量逐步降低,合金的最大放电容量由x=0.05时的383.43 mAh/g下降到x=0.3时的348.40 mAh/g;而合金的高倍率放电性能呈现先增后减的趋势,当电流密度为900 mA/g时,合金的高倍率放电性能由83.66%(x=0)增加到92.57%(x=0.05)然后减小到83.9%(x=0.3);循环稳定性先增加后下降,当x=0.1时合金电极的循环寿命达到最大(S100=74.71%).     

LaNi_(3.15-x)Mn_xCo_(0.25)Al_(0.1)储氢合金结构及电化学性能

为了研究Mn替代Ni对AB3.5型储氢合金结构及电化学性能的影响,采用电弧炉熔炼制备LaNi3.15-xMnxCo0.25Al0.1合金。采用XRD、SEM等材料分析方法以及恒电流充放电等电化学测试技术,研究LaNi3.15-xMnxCo0.25Al0.1(0≤x≤0.3)合金的结构和电化学储氢性能。结果表明:LaNi3.15-xMnxCo0.25Al0.1(0≤x≤0.3)合金由多相组合形成,合金的主相为LaNi5和La2Ni7;随着Mn替代Ni含量的增加,LaNi5相中a轴和c轴以及晶胞体积增加;合金电极的最大放电容量有所升高,由x=0的238mA·h/g逐渐增加到x=0.3的277.1mA·h/g;高倍率性能随着Mn含量的增加先升高后降低,在x=0.2时合金的高倍率性能最佳。     

Influence of substituting Ni with Co on hydriding and dehydriding kinetics of melt spun nanocrystalline and amorphous Mg2Ni-type alloys

In order to improve the hydriding and dehydriding kinetics of the Mg₂Ni-type alloys, Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg₂Ni-type Mg₂Ni_1−x Co _x (x=0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied with an X-ray diffractometer (XRD) and a high resolution transmission electronic microscope (HRTEM). An investigation on the thermal stability of the as-spun alloys was carried out with a differential scanning calorimeter (DSC). The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results demonstrate that the substitution of Co for Ni does not alter the major phase of Mg₂Ni but results in the formation of secondary phase MgCo₂. No amorphous phase is detected in the as-spun Co-free alloy, but a certain amount of amorphous phase is clearly found in the as-spun Co-containing alloys. The substitution of Co for Ni exerts a slight influence on the hydriding kinetics of the as-spun alloy. However, it dramatically enhances the dehydriding kinetics of the as-cast and spun alloys. As Co content (x) increases from 0 to 0.4, the hydrogen desorption capacity increases from 0.19% to 1.39% (mass fraction) in 20 min for the as-cast alloy, and from 0.89% to 2.18% (mass fraction) for the as-spun alloy (30 m/s).     

贮氢合金La-Mg-Ni系的贮氢性能

借助X-ray及吸氢性能测试装置研究了AB3型La-Mg-Ni系贮氢合金的结构和贮氢性能,测试了不同温度下合金的PCT曲线.结果表明,La-Mg-Ni系贮氢合金可获得(La,Mg)Ni3相组织;加Co,改善了合金的特性,并使平台压力降低.     

LaNi_（3.8）Co_（1.1）Mn_（0.1）/TiMn_（1.5）贮氢合金的结构和性能

为了探索一种新的掺杂方式对AB5型贮氢合金贮氢性能的影响,采用熔炼掺杂方法制备La-Ni3.8Co1.1Mn0.1/TiMn1.5（TiMn1.5质量分数为4%、8%）贮氢合金,利用PCTPro-2000气体吸附测量仪研究了合金的气态储氢性能。XRD和SEM分析显示,熔炼掺杂后合金主相为LaNi5相,出现少量（NiCo）3Ti相。P-C-T测试结果表明,（NiCo）3Ti相的出现对合金气态贮氢性能有较大影响,熔炼掺杂后合金吸放氢平台压和滞后效应降低,贮氢容量减少。掺杂TiMn1.5使得合金的氢化物的生成焓由原始合金的-27.35kJ/mol降至-29.14kJ/mol（掺杂质量分数8%的TiMn1.5）,较高温度有利于合金中氢的释放,同时掺杂形成的（NiCo）3Ti相改善了合金吸/放氢动力学性能。     

Effects of alloying side B on Ti-based AB2 hydrogen storage alloys

Ti-based AB2-type hydrogen storage alloys are a group of promising materials, which will probably replace the prevalent rare earth-based AB5-type alloys and be adopted as the main cathode materials of nickelmetal hydride (Ni-MH) batteries in the near future. Alloying in side B is a major way to improve the performance of Ti-based AB2-type alloys. Based on recent studies, the effects of alloying elements in side B upon the performance of Ti-based AB2-type hydrogen storage alloys are systematically reviewed here. These performance sare divided into two categories, namely PCI characteristics, including hydrogen storage capacity (HSC), plateau pressure (PP), pressure hysteresis (PH) and pressure plateau sloping (PPS), and electrochemical properties, including discharge capacity (DC), activation property ( AP), cycling stability (CS) and high-rate dischargeability (HRD). Furthermore, the existing problems in these investigations and some suggestions for future research are proposed.     

MgH2-graphene复合储氢材料吸放氢性能

通过球磨制备MgH2,MgHz-GMgHz-graphene储氢材料,研究石墨烯添加对MgH2吸放氢性能的影响。结果表明,石墨和石墨烯对球磨过程中MgHz的细化有促进作用;石墨和石墨烯的添加对MgH2的吸放氢动力学有良好的改善作用;特别是MgH2-graphene储氢材料有优良的吸放氢性能,在573K下于5,2min内放氢和再吸氢质量分数都为7．0％,且其放氢起始温度较MgH2的低50K。     

La1-xCexNi3.54Co0.78Mn0.35Al0.32贮氢合金相结构和电化学性能的研究

采用真空电弧熔炼和热处理方法制备了La1-xCexNi3.54Co0.78Mn0.35Al0.32(x=0.1,0.2,0.3,0.4,0.5,0.6)贮氢合金.X射线衍射(XRD)分析表明,合金含有单一CaCu5型六方结构相.电化学性能测试表明,随着x的增加,合金的最大放电容量从348.1mAh/g(x=0.1)单调地减小到310.1 mAh/g(x=0.6);HRD1200先从28.6%(x=0.1)增加到65.4%(x=0.5)然后降低到60.1%(x=0.6),归因于合金表面的电催化活性和合金体内氢原子扩散速率均随x的增大先增大后减小.     

稀土-镁-镍基贮氢合金的研究进展

综述了近几年稀土-镁-镍基贮氢合金电极材料相结构与电化学性能等方面的研究进展。介绍了改善合金电化学性能的方法,包括合金组成的改进、热处理、表面处理、制备复合合金等方法。讨论了稀土-镁-镍基贮氢合金研究中的几个重要问题以及发展方向。