Research of heat treatment of low-Co AB_5 type hydrogen storage alloys for MH-Ni batteries

The effects of low-Co AB_5 type hydrogen storage alloys prepared by quenchingand annealing on the performances of MH-Ni batteries were investigated, and the characteristics ofthe low-Co AB_5 type hydrogen storage alloys were compared with those of the high-Co AB_5 typehydrogen storage alloy as well. The results showed that the faster the cooling of the low-Cohydrogen storage alloy is, the better homogeneity of the chemical composition for the alloy and thelonger cycle life of the battery are, but the electrochemical discharge capacity and high-ratedischarge ability are reduced. The high-rate discharge ability and charge retention of MH-Nibatteries for the conventional as-cast annealed low-Co hydrogen storage alloy were superior to thosefor the rapidly quenched low-Co hydrogen storage alloy and the high-Co hydrogen storage alloy, buta little inferior in the cycle life.

AB_5-type Hydrogen Storage Alloy Modified with Ti/Zr Used as Anodic Materials in Borohydride Fuel Cell

Fuel cell using borohydride as the fuel has received much attention. AB5-type hydrogen storage alloy used as the anodic material instead of noble metals has been investigated. In order to restrain the generation of hydrogen and enhance the utilization of borohydride, Ti/Zr metal powders has been added into the parent LmNi4.78Mn0.22 （where Lm is La-richened mischmetal） alloy （LNM） by ball milling and heat treatment methods. It is found that the addition of Ti/Zr metal powders lowers the electrochemical catalytic activity of the electrodes, at the same time, restrains the generation of hydrogen and enhances the utilization of the fuel. All the results show that the hydrogen generation rate or the utilization of the fuel is directly relative to the electrochemical catalytic activity or the discharge capability of the electrodes. The utilization of the fuel increases with discharge current density. It is very important to find a balance between the discharge capability and the utilization of the fuel.

Phase structure and electrochemical properties of La_(0.7)Ce_(0.3)Ni_(3.75)Mn_(0.35)Al_(0.15)Cu_(0.75-x)Fe_x hydrogen storage alloys

La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-xFex （x=0-0.20） hydrogen storage alloys were synthesized by induction melting and subsequent annealing treatment, and phase structure and electrochemical characteristics were investigated. All alloys consist of a single LaNi5 phase with CaCu5 structure, and the lattice constant a and the cell volume （V） of the LaNi5 phase increase with increasing x value. The maximum discharge capacity gradually decreases from 319.0 mA？h/g （x=0） to 291.9 mA？h/g （x=0.20） with the increase in x value. The high-rate dischargeability at the discharge current density of 1200 mA/g decreases monotonically from 53.1% （x=0） to 44.2% （x=0.20）. The cycling stability increases with increasing x from 0 to 0.20, which is mainly ascribed to the improvement of the pulverization resistance.

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 AB(2) and AB(5) 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 AB(5) 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.

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 similar to 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-east 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-east 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 similar to 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.

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.

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.

Effect of B and Fe substitution on structure of AB_3-type Co-free hydrogen storage alloy

A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys were characterized by XRD,EDS and SEM to investigate the effects of B and Fe substitution for Ni on material structure.The content of LaMg2Ni9 phase within La0.7Mg0.3Ni3 alloy reaches 37.9% and that of La0.7Mg0.3Ni2.9(FeB)0.1 alloys reduces to 23.58%.Among all samples,ground particles with different shapes correspond to different phases.The major substitution occurs in LaMg2Ni9 phase.Electrochemical tests indicate that substituted alloys have different electrochemical performance,which is affected by phase structures of alloy.The discharge capacity of La0.7Mg0.3Ni3 alloy reaches 337.3 mA·h/g,but La0.7Mg0.3Ni2.9(FeB)0.1 alloy gets better high rate discharge(HRD) performance at the discharge rate of 500 mA/g with a high HRD value of 73.19%.

Phase structure and electrochemical properties of La_(1.7+x)Mg_(1.3-x)(NiCoMn)_(9.3)(x=0-0.4) hydrogen storage alloys

The phase structure and electrochemical properties of La1.7＋xMg1.3-x（NiCoMn）9.3（x=0-0.4） alloys were investigated. The XRD analysis reveals that the alloys consist of LaNi5 phase and other phases, such as LaMg2Ni9 phase （PuNi3 structure） and La4MgNi19 phases （Ce5Co19＋Pr5Co19 structure, namely A5B19 type）. With the increase of the x value, the LaMg2Ni9 phase fades away and La4MgNi19 phases appear, while the abundance of LaNi5 phase firstly increases and then decreases. At the same time, the cell volume of LaNi5 phase and LaMg2Ni9 phase decreases. The electrochemical measurement shows that alloy electrodes could be activated in 4-5 cycles, and with the increase of the x value, the maximum discharge capacity gradually increases from 330.9 mA-h/g （x=0） to 366.8 mA-h/g （x=0.4）, but the high-rate dischargeability （HRD） and cyclic stability （S） decrease somewhat （x=0.4, HRD600=82.32%, S100=73.8%）. It is found that the HRD is mainly controlled by the electrocatalytic activity on the alloy electrode surface, and the decline of cyclic stability is due to the appearance of A5B19 type phase with larger hydrogen storage capacity, which leads to larger volume expansion and more intercrystalline stress and then easier pulverization during charging/discharging.

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 electrochemical 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.

Electronic Structure of Hydrogen Storage Compounds, LaNi_5 and Its Micro-Hydrogenated Compounds

The electronic structures of LaNi5 hydrogen storage alloys and its micro-hydrogenated compounds with two hydrogen atoms in the center of two octahedral interstices and two tetrahedral interstices, were investigated by the first principles discrete variational method （DVM）. The results of density of states and the difference of charge distribution clearly show that the s electrons of H mainly interact with the s electrons of hydride-non-forming element Ni, despite there being a larger affinity of La for hydrogen than that of Ni in pure metal-hydrogen system. From the cohesive energy of systems, we also found two systems have almost same stability with occupation of H atoms.

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.

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.

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。