The electrochemical characteristics of AB_(4)-type rare earth-Mg-Ni-based superlattice structure hydrogen storage alloys for nickel metal hydride battery

Rare earth-Mg-Ni-based alloys with superlattice structures are new generation negative electrode materials for the nickel metal hydride batteries.Among them,the novel AB_(4)-type superlattice structure alloy is supposed to have superior cycling stability and rate capability.Yet its preparation is hindered by the crucial requirement of temperature and the special composition which is close to the other superlattice structure.Here,we prepare rare earth-Mg-Ni-based alloy and study the phase transformation of alloys to make clear the formation of AB_(4)-type phase.It is found Pr_(5)Co_(19)-type phase is converted from Ce_(5)Co_(19)-type phase and shows good stability at higher temperature compared to the Ce_(5)Co_(19)-type phase in the range of 930-970℃.Afterwards,with further 5℃increasing,AB_(4)-type superlattice structure forms at a temperature of 975℃by consuming Pr_(5)Co_(19)-type phase.In contrast with A_(5)B_(19)-type alloy,AB_(4)-type alloy has superior rate capability owing to the dominant advantages of charge transfer and hydrogen diffusion.Besides,AB_(4)-type alloy shows long lifespan whose capacity retention rates are 89.2%at the 100;cycle and 82.8%at the 200;cycle,respectively.AB_(4)-type alloy delivers 1.53 wt.%hydrogen storage capacity at room temperature and exhibits higher plateau pressure than Pr_(5)Co_(19)-type alloy.The work provides novel AB_(4)-type alloy with preferable electrochemical performance as negative electrode material to inspire the development of nickel metal hydride batteries.

Crystal structure and hydrogen storage properties of(La,Ce)Ni_(5-x)M_x(M = Al, Fe, or Co) alloys

The effects of partial substitution of La by Ce and Ni by Al, Fe, or Co in LaNi_5-based alloys on hydrogen storage performance were systematically studied. All samples were prepared using vacuum arc melting in an argon atmosphere. The results showed that for LaNi_(5-x)M_x(M = Al, Fe, or Co) alloys, the lattice constants and unit cell volumes increased with an increasing amount of Al and Fe. On the other hand, these parameters decreased upon partial substitution of La by Ce. In addition, the lattice constant remained almost constant in the La_(0.6)Ce_(0.4)Ni_(5–x)Cox alloys regardless of the value of x(x = 0.3, 0.6, or 0.9), as Ce might enhance the homogeneity of the CaCu_5-type phase in Co-containing alloys. The hydrogen storage properties of the alloys were investigated using pressure, composition, and temperature isotherms. The experimental results showed that the plateau pressure decreased with an increasing content of Al, Fe, or Co, but it increased with Ce addition. Furthermore, the plateau pressures of all Co-containing alloys were almost identical upon substitution with Ce. Finally, the enthalpy(ΔH) and entropy(ΔS) values for all alloys were calculated using van't Hoff plots. The relationship between the lattice parameters and enthalpy changes for hydrogenation will be discussed.

Effects of Strip Casting and Annealing on Electrochemical Properties of LPCNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) Hydrogen Storage Alloys

The effect of thickness （1～10 mm） of the ingots on the electrochemical properties of as-cast and annealed strip cast LPCNi3.55Co0.75Mn0.4Al0.3 hydrogen storage alloys was investigated. It is found that the 0.2 C discharge capacity of as-cast LPCNi3.55Co0.75Mn0.4Al0.3 alloy increases with the increase of the thickness of the ingots. As-cast alloy with the thickness of 10 mm shows better activation property, higher 1C discharge capacity and better cyclic stability than others. It is mainly contributed to its larger unit cell volume and less internal stress. Annealed LPCNi3.55Co0.75Mn0.4Al0.3 alloy with the thickness of 3 mm shows much better comprehensive electrochemical properties than as-cast one; The cyclic stability of the alloy with the thickness of 6 mm and the activation properties of the alloys with the thickness of 3～6 mm are improved after annealing. It is mainly owing to the great release of internal stress and the decrease of the segregation of Mn in the alloys.

Electrochemical Properties of Strip Casting LPCNi_(3.55) Co_(0.75) Mn_(0.4) Al_(0.3) Hydrogen Storage Alloys

LPCNi 3.55 Co 0.75 Mn 0.4 Al 0.3 hydrogen storage alloy was investigated, and the effects of thickness of its strip casting ingots(as cast) on the electrochemical performances were discussed. It was found that the 0.2 C discharge capacity increased with the increase of the thickness (from 1 mm to 10 mm) of the ingots, mainly due to the enlargement of the unit cell volume; Among the thickness of the ingots in our study, 10 mm sample showed a better activation property; LPCNi 3.55 Co 0.75 Mn 0.4 Al 0.3 alloy with 10mm showed higher comprehensive properties than those with other thickness under 1C rate.

Surface Modification of AB_2 and AB_5 Hydrogen Storage Alloy Electrodes by the Hot-Charging Treatment

The effect of the hot-charging treatment on the performance of AB2 and AB5 hydrogen storage alloy electrodes was investigated. The result showed that the treatment can markedly improve the voltage plateau ratio (VPR), the high rate discharge ability (HRDA), the diffusion coefficient of hydrogen DH and the discharge capacity of the AB2 hydrogen storage alloy electrode. The SEM analysis showed that the hot-charging treatment brings about a Ni-rich surface due to the dissolution of Zr oxides. It is also very helpful for the improvement of the kinetic properties of AB2 hydrogen storage alloy electrode because the microcracking of the surface results in fresh surface. This can be the basic modification treatment for NiMH battery used in electric vehicles (EVs) in the future. But for AB5 type alloys, the treatment has the disadvantage of impairing the comprehensive electrochemical properties, because the surface of the alloy may be corroded during the treatment. The mechanism of the surface modification of the electrode is also proposed.

Microstructure and electrochemical properties of LaNi_(4-x)FeMn_x (x=0-0.8) hydrogen storage alloys

In order to reduce the cost of LaNi5 based hydrogen storage alloys, effect of substitution of Mn for Ni on structural and electro-chemical properties of LaNi4-xFeMnx (x=0-0.8) hydrogen storage alloys was studied systematically. X-ray diffraction (XRD) and scanning electron microscope (SEM) showed that LaNi5 and La2Ni7 phases were invariably present in all alloy samples, and when x≥0.4, (Fe, Ni) phase was observed. Electrochemical studies revealed that the discharge capacity reached a maximum value of 306.4 mAh/g when x=0.2 and the cycling stability decreased with the increase of x. With the increase of Mn content, hydrogen diffusion coefficient decreased, whereas high rate discharge-ability (HRD) and exchange current density first increased slowly when x≤0.2 and then decreased markedly when x=0.8, indicating that electrochemical reaction on the surface of alloy electrodes had strong influence on kinetic property.

Structure and electrochemical performance of hydrogen storage alloy La_(0.7)Mg_(0.3)Ni_(2.875)Co_(0.525)Mn_(0.1)-boron composite

The structure and electrochemical characteristics of La0.7Mg0.3Ni2.875Co0.525Mn0.1-boron composite was studied systematically. The AB3 type hydrogen storage alloys La0.7Mg0.3Ni2.875Co0.525Mn0.1 were successfully synthesized by means of inter-media alloy La2Mg17. The alloys were composited with boron at different weight rate. From the XRD analyses, each alloy of this series is mainly composed of (La,Mg)Ni3 phase and the LaNi5 phase, and the phase abundance of each phase varies with the boron weight rate, moreover, after composition, the c and cell volumes of (La,Mg)Ni3 phase increase, and the LaNi5 phase keep the same, which indicate that the boron may enter (La,Mg)Ni3 phase. The electrochemical studies show that the maximum discharge capacity of the composites decreases, but the cycling life improved. And the high rate discharge ability and exchange impendence spectroscopy (EIS) of the AB3 alloys and its composite were also studied.

CHARACTERISTICS OF METAL-HYDROGEN INTERACTION IN HYDROGEN STORAGE ALLOYS

The electronic structures are calculated by the DV-Xa molecular orbital method employing small model clusters in order to clarify the roles of the hydride forming elements, A, (e.g., La, Zr Ti, Mg) and non-forming elements, B, (e.g., Ni, Mn, Fe) in hydrogen storage alloys. It is confirmed from this calculation that hydrogen interacts more strongly with hydride non-forming elements, B, than hydride forming elements, A, in agreement with our previous calculations. However,the B-H interaction is enhanced only when some A element exists in the neighborhood. Otherwise, such a B-H interaction never operates in the alloy. In this sense,the coexistence of A and B elements are essential in the constitution of hydrogen storage alloys. Also, it is shown that the A/B compositional ratio of hydrogen storage alloys is understood in terms of a simple parameter, 2Bo(A - B) / /Bo(A - A)+ Bo(B-B)], where the Bo(A-B), Bo(A-A) and the Bo(B-B) are the bond strengths between atoms given in the parentheses.

Effect of Fe and Cu on Electrochemical Characteristics of Low-Co AB5 Type Alloys

In order to further reduce the cost of AB5 type rare earth-based hydrogen storage alloy, a low-Co AB5 type hydrogen storage alloy were by substituting Co with Cu and Fe.The characteristics of these alloys have been investigated by means of XRD, PCT, and measurement of electrochemical capacity and cycle life.The test results show that the effect of these two kinds of substituting elements on discharge capacity is Cu ＞ Fe, and the cycle life is on the contrary.Both of them have no distinct influence on activity speed, but activity speed increases with the decrease of Co.By the order way, the high discharge rate characteristics rise with the addition of Cu and decreasing of Co.

Microstructure and Hydrogen Absorption Pro-perties of Mg/MmNi_(5-x) (CoAlMn)_x Composite Prepared by Mechanical Alloying

The microstructure ofthe Mg/MmNi5-x (CoAlMn )x composite hydrogen storage material preparedby the method of mechanical alloyingwas characterized by X-ray diffraction, SEM and particle size distribution analysis. By measuring PCTcurves, the hydrogen absorption properties of the composite was evaluated.The results show that nanocrystallinecomposite structure can be obtainedunder adequate ball milling condition. The reactive activation and hydrogen absorption capacity are improved compared with the sole MmNi5-x(CoAlMn)x alloy. The effect ofmagnesium on the microstructure andhydrogen absorption properties of thecomposite were also evaluated.

Phase forming law and electrochemical properties of A2B7-type La-Y-Ni-based hydrogen storage alloys with different La/Y ratios

The effects of different proportions of La and Y elements in the A-side on the structure and properties of A_(2)B_(7)-type La-Y-Ni hydrogen storage alloys were investigated.The(La,Y)_(2)Ni_(7)hydrogen storage alloys with different La/Y ratios were prepared by sintering the Y_(2)Ni_(4)precursor and different AB_(5)-type precursors at 1298 K for 5 h and subsequently annealed for 20 h at 1248 K.All the alloys only contain Ce_(2)Ni_(7)(2H-type)and Gd_(2)Co_(7)(3R-type)phases with different mass ratios.As the La/Y ratio decreases,the cell volume of the two phases declines and the corresponding plateau pressure gradually increases.As the proportion of Y in the alloy increases,the hydrogen storage capacity increases gradually from 1.309 wt%(La/Y=1/1)to 1.713 wt%(La/Y=1/5)and the high-rate discharge(HRD1500)ability of the alloy electrodes increases gradually from 62.7%(La/Y=1/1)to 88.6%(La/Y=1/5).The hydrogen diffusion rate in the bulk of the alloy is the controlling step of hydriding/dehydriding kinetics.The Y ele ment can effectively inhibit the hydrogen-induced amorphous(HIA)of La-Y-Ni alloys,but the poor stability of the Y element in alkaline KOH aqueous solution leads to a decrease in the electrochemical cyclic stability with increasing Y content.

高倍率AB_5型稀土贮氢合金的研究进展

综述了AB5型稀土贮氢合金高倍率放电性能的影响因素。从合金成分、制备工艺、粒度控制以及表面改性等几个方面进行总结 ,并对贮氢合金高倍率放电机制等问题进行了讨论。开发低钴无钴系列合金、非化学计量比、形成双相合金、控制粒度分布以及表面改性处理是目前改善AB5型稀土贮氢合金高倍率放电性能的有效途径。

硼对低钴AB_5型贮氢合金循环寿命的影响

为了提高低钴 AB_5 型贮氢合金的电化学循环稳定性,在低钴 AB_5 型贮氢合金中加入微量的硼,用真空快淬工艺制备了稀土系低钴 AB_5型 MmNi_(3.8)Co_(0.4)Mn_(0.6)Al_(0.2)Bx_(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微观结构及循环寿命的影响。结果表明,硼能大幅度提高铸态及快淬态低钴 AB5型贮氢合金的电化学循环稳定性,但其作用机理是完全不同的。

高性能AB_5型贮氢合金的成分设计

贮氢合金是MH -Ni电池技术的核心 ,而其化学成分是决定贮氢合金性能的主要因素。在分析MH -Ni电池对负极材料的性能要求及电极失效机理的基础上 ,详细讨论了AB5型贮氢合金的主要电化学性能与各种合金元素之间的关系 。

快淬工艺对无钴AB_5型贮氢合金循环稳定性的影响

研究了快淬工艺对无钴AB5型LaxMm1-x(NiMnSiAlFe)4.9(x=0,0.45,0.75,1.0)合金微观结构及电化学循环稳定性的影响。结果表明:快淬处理显著改善合金的成分均匀性,使晶粒细化,并显著提高合金的循环稳定性。当淬速从0m/s增加到28m/s时,经300次充放循环后,x=0.45合金的容量衰减率D从0.28mAh/g·c-1(c代表一次循环)下降到0.13mAh/g·c-1;x=1.0合金的容量衰减率D从0.3mAh/g·c-1下降到0.14mAh/g·c-1。

Fe替代Co对AB_5型电极合金微观结构及电化学性能的影响

用铸造及快淬工艺制备了稀土基AB5型Mm(NiMnSiAl)4.3Co0.6-xFex(x=0、0.1、0.2、0.3、0.4、0.5、0.6)贮氢电极合金,测试了合金在铸态及快淬态下的微观结构与电化学性能。研究了Fe替代Co对铸态及快淬态贮氢合金微观结构及电化学性能的影响。研究结果表明,Fe替代Co对铸态及快淬态合金的相结构没有明显影响,但对合金的电化学性能产生显著影响。对铸态及快淬态合金,随Fe替代量的增加,合金的容量下降,但合金的循环寿命得到不同程度的改善。Fe替代Co对快淬态合金循环寿命的改善更加显著,导致这一结果的主要原因是Fe替代Co使快淬态合金的微观组织显著细化。

AB_5型贮氢合金及其优化设计

AB5型贮氢合金的性能主要取决于其成分、结构和显微组织。本文从AB5型贮氢合金的晶体结构出发 ,详细讨论了AB5型贮氢合金在诸多方面的优化措施 :(1)化学成分上 ,向多元合金化发展 ,降低合金的成本 ,改善合金性能 ;(2 )结构上 ,偏离AB5结构 ,发展非化学计量比合金 ;(3)显微组织上 ,从主相向“主相 +辅相”发展 ;(4 )工艺上 ,开发新的合金制备、热处理和表面改性等工艺方法 ;(5 )改善合金使用环境 ;(6 )研究方法上理论化、系统化。通过这些途径 ,可以对AB5型贮氢合金进行深入研究 ,进一步提高合金的性能。

AB_5型储氢合金初始放电容量的预测

将模拟退火算法用于神经网络,对AB5_型储氢合金的初始放电容量性能进行预测。通过实验确定了冷却进度表中各项参数并讨论了其对网络预测性能的影响,提出了实用的冷却制度;将模拟退火算法与传统的梯度下降法结合,用于人工神经网络的优化与预测,得到了预测效果等与迭代时间性能更好的神经网络。

利用表面修饰提高AB_5型贮氢电极性能

贮氢合金的表面性质对于它的电化学应用十分重要。AB5病型贮氢合金虽然具有活化性能好 ,容量在2 6 0mA·h/g～ 32 0mA·h/g是目前生产MH Ni电池负极的主干材料。但是AB5,型贮氢合金在反复充放电过程中抗氧化和抗粉化的能力很差 ,导致放电容量的迅速降低。综述和比较了近年来对AB5,型贮氢合金表面处理的研究情况 。