Rare earth-Mg-Ni-based hydrogen storage alloys as negative electrode materials for Ni/MH batteries

This review is devoted to new rare earth-Mg-Ni-based (R-Mg-Ni-based) hydrogen storage alloys that have been developed over the last decade as the most promising next generation negative electrode materials for high energy and high power Ni/MH batteries. Preparation techniques, structural characteristics, gas-solid reactions and electrochemical performances of this system alloy are systematically summarized and discussed. The improvement in electrochemical properties and their degradation mechanisms are covered in detail. Optimized alloy compositions with high discharge capacities, good electrochemical kinetics and reasonable cycle lives are described as well. For their practical applications in Ni/MH batteries, however, it is essential to develop an industrial-scale homogeneous preparation technique, and a low-cost R-Mg-Ni-based electrode alloy (low-Co or Co-free) with high discharge capacity, long cycle life and good kinetics.     

Microstructure and electrochemical properties of low-temperature hydrogen storage alloy used in Ni/MH batteries

AB5 hydrogen storage alloys La0.54Ce0.28Pr0.18Ni4-xCo0.6Mno35Alx （x=0.1, 0.2, 0.3） were prepared by arc melting method under an Ar atmosphere. The results show that the contents of Ni and Al have obvious influences on the microstructure and electrochemical properties of the alloys. Both the lattice parameters and the cell volumes decrease with decreasing x value. Moreover, the discharge capacity at different temperatures, the high rate discharge property, and the cycling life of the alloy electrode are also in close relationship with the x value. When x value increases from 0.1 to 0.3, the discharge capacities with a discharge current density of 60 mA/g slightly decreases at 25℃, but evidently deteriorates at -40℃, the high-rate property gravely decreases, and the cycle life of the alloy electrode is improved in some extent. Therefore, it is meaningful to control Al content for the AB5 hydrogen storage alloys used in Ni/MH batteries.     

低钴AB_5型贮氢合金的制备及电化学性能

为了降低镍氢电池的原材料成本 ,研究了一系列多元、低钴和无钴AB5型贮氢合金 ,以及取代元素对贮氢合金电化学性质的影响。结果显示 ,用少量的铁、铜和铬部分取代贮氢合金La(NiMnCoAl) 5中的钴对改善贮氢合金电化学循环稳定性有效。贮氢合金La(NiMnAl) 4.6(FeCuCr) 0 .2 Co0 .2 具有满意的循环稳定性 ,它在 0 .2C放电条件下的最大放电容量为 2 96mAh/g-1,经过 30 0次循环容量衰减仅 2 1.8%。另外 ,还用X射线衍射检测了贮氢合金的微观结构     

The effect of Nd content on the electrochemical properties of low-Co La–Mg–Ni-based hydrogen storage alloys

The low-Co content La_0.80−xNd_xMg_0.20Ni_3.20Co_0.20Al_0.20 (x = 0.20, 0.30, 0.40, 0.50, 0.60) alloys were prepared by inductive melting and the effect of Nd content on the electrochemical properties was investigated. XRD shows that the alloys consist mainly of LaNi₅ phase, La₂Ni₇ phase and minor LaNi₃ phase. The electrochemical P–C–T test shows hydrogen storage capacity increases first and then decreases with increasing x, which is also testified by the electrochemical measurement that the maximum discharge capacity increases from 290 mAh/g (x = 0.20) to 374 mAh/g (x = 0.30), and then decreases to 338 mAh/g (x = 0.60). The electrochemical kinetics test shows exchange current density I₀ increases with x increasing from 0.20 to 0.50 followed by a decrease for x = 0.60, and hydrogen diffusion coefficient D increases with increasing x. Accordingly high rate dischargeability increases with a slight decrease at x = 0.60 and the low temperature dischargeability increases with increase in Nd content. When x is 0.50, the alloy exhibits a better cycling stability.     

La0.8-χREχMg0.2Ni3.2CO0.6储氢合金的结构及电化学性能

通过感应容炼制备了La0.8-xREMg0.2Ni3.2Co0.6(RE=Sm,Dy,0≤x≤0.3)合金.采用X射线衍射分析了该合金的晶体结构,并研究了其电化学性能.结果表明该合金是由LaNi5主相和LaNi3第二相构成;随着Sm(Dy)取代La量的增加,合金主相单胞体积线性收缩,合金储氢量和放电容量减小,当Sm(Dy)取代量分别为0.1、0.2、0.3时,合金容量由380 mA·h/g分别减小到370(362)、355(334)、329(295)mA·h/g,但高倍率放电能力和循环稳定性得到改善,100次循环后的容量损失率由20%分别降低到18%(17%)、16%(14%)、13%(11%).     

Fabrication characteristics and hydrogenation behavior of hydrogen storage alloys for sealed Ni−MH batteries

Hydrogen storage alloys based on LmNi_4.2Co_0.2Mn_0.3Al_0.3 were fabricated to study the equilibrium hydrogen pressure and electrochemical performance. The surface morphology and structure of the alloys were analyzed by SEM and XRD, and then the hydrogenation behaviors of all alloys were evaluated by PCT and electrochemical half-cell. We studied the hydrogenation behavior of the Lm-based alloy with changes in composition elements such as Mn, Al, and Co and investigated the optimal design for Lm-based alloy in a sealed battery system. As a result of studying the hydrogenation characterization of alloys with the substitution elements, hydrogen storage alloys such as LmNi_3.75Co_0.15Mn_0.5Al_0.3 and LmNi_3.5Co_0.5Mn_0.5Al_0.5 were obtained to correspond with the characteristics of a sealed battery with a higher capacity, long life cycle, lower internal pressure, and lower battery cost. The capacity preservation rate of LmNi_3.5Co_0.5Mn_0.5Al_0.5 was greatly improved to 92.7% (255 mAh/g) at 60 cycles, indicating a low equilibrium hydrogen pressure of 0.03 atm in PCT devices.     

热处理温度对LaNi3.8Al1Mn0.2合金储氢性能的影响

对热处理(1173K, 1223K, 1273K, 1323K)前后LaNi3.8Al1.0Mn0.2合金的研究表明,热处理前后合金均由一个主相,三种第二相组成。热处理后第二相后变小,分布更加弥散,第二相中LaNi2变为LaNi相,晶胞参数和晶胞体积增加,活化性能变差,但吸放氢平台压降低,吸放氢平台的斜率和滞后变小,合金的吸氢速度显著变快,吸放氢焓变和吉布斯自由能的绝对值增大,而吸氢量未见明显变化。随着热处理温度的升高,晶胞参数和晶胞体积先增大后减小,吸放氢平台压先降低后升高,斜率先增大后减小,滞后先减小后增大,而焓变和自由能的绝对值先增加后减小,在1223K分别达到最大和最小值,而热处理温度的升高使活化性能和动力学性能略有提升。     

Structure and electrochemical properties of the Fe substituted Ti–V-based hydrogen storage alloys

To elucidate the effects of Fe on the Ti–V-based hydrogen storage electrode alloys, the Ti_0.8Zr_0.2V_2.7−xMn_0.5Cr_0.8Ni_1.0Fe_x (x = 0.0–0.5) alloys were prepared and their structures and electrochemical properties were systematically investigated. XRD results show that all the alloys consist of a C14 Laves phase with hexagonal structure and a V-based solid solution phase with bcc structure. With increasing Fe content, the abundance of the C14 Laves phase gradually decreases from 43.4 wt% (x = 0.0) to 28.5 wt% (x = 0.5), on the contrary, that of the V-based solid solution phase monotonously increases from 56.6 wt% to 71.5 wt%. In addition, SEM observation finds that the grain size of the V-based solid solution phase is first gradually reduced and then enlarged with increasing x. Electrochemical investigations indicate that the substitution of Fe for V markedly improves the cycling stability and the high rate dischargeability of the alloy electrodes, but decreases the maximum discharge capacity and the activation performance. Further electrochemical impedance spectra, the linear polarization curve and the potentiostatic step discharge measurements reveal that the electrochemical kinetics of the alloy electrodes should be jointly controlled by the charge-transfer reaction rate on the alloy surface and the hydrogen diffusion rate in the bulk of the alloys. For the alloy electrodes with the lower Fe content (x = 0.0–0.2), the hydrogen diffusion in the bulk of the alloys should be the rate-determining step of its discharge process, and while x increases from 0.3 to 0.5, the charge-transfer reaction on the alloy surface becomes to the rate-determining step, which induces that the electrochemical kinetics of the alloy electrodes is firstly improved and then decreased with increasing Fe content.     

Effects of annealing treatment on the microstructure and electrochemical properties of low-Co hydrogen storage alloys containing Cu and Fe

The effects of annealing treatment on the microstructure and electrochemical properties of low-Co LaNi_3.55Mn_0.35Co_0.20Al_0.20Cu_0.75Fe_0.10 hydrogen storage alloys were investigated. X-ray diffraction (XRD) analysis indicated that annealing treatment remarkably reduced the lattice strain and defects, and increased the unit-cell volume. The optical microscope analysis showed that the as-cast alloy had a crass dendrite microstructure with noticeable composition segregation, which gradually disappeared with increasing annealing temperature, and the microstructure changed to an equiaxed structure after annealing the alloy at 1233 K. The electrochemical tests indicated that the annealed alloys demonstrated much better cycling stability compared with the as-cast one. The capacity retention at the 100th cycle increased from 90.0% (as-cast) to 94.7% (1273 K). The annealing treatment also improved the discharge capacity. However, the high rate dischargeability (HRD) value of the annealed alloy slightly dropped, which was believed to be ascribed to the decreased exchange current density and the hydrogen diffusion coefficient in alloy bulk.     

Effects of annealing treatment on the microstructure and electrochemical properties of low-Co hydrogen storage alloys containing Cu and Fe

The effects of annealing treatment on the microstructure and electrochemical properties of low-Co LaNi3.55Mno.35Co0.20Al0.20Cuo.75Fe0.10 hydrogen storage alloys were investigated.X-ray diffraction (XRD) analysis indicated that annealing treatment remarkably reduced the lattice strain and defects,and increased the unit-cell volume.The optical microscope analysis showed that the as-cast alloy had a crass dendrite microstructure with noticeable composition segregation,which gradually disappeared with increasing annealing temperature,and the microstructure changed to an equiaxed structure after annealing the alloy at 1233 K.The electrochemical tests indicated that the annealed alloys demonstrated much better cycling stability compared with the as-cast one.The capacity retention at the 100th cycle increased from 90.0％(as-cast) to 94.7％ (1273 K).The annealing treatment also improved the discharge capacity.However,the high rate dischargeability (HRD)value of the annealed alloy slightly dropped,which was believed to be ascribed to the decreased exchange current density and the hydrogen diffusion coefficient in alloy bulk.     

Effects of chemical coating with Ni on electrochemical properties of Mg2Ni hydrogen storage alloys

The effects of nickel coating on the electrochemical properties of Mg2Ni hydrogen storage alloys are presented in this paper. X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques were employed to examine the crystal structure and surface morphologies of the bare and Ni-coated Mg2Ni alloys. The electrochemical properties of alloys were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that Ni coating not only decreased the charge transfer resistance, but also decreased the H atom diflusion resistance for Mg2Ni alloys. It was also found that Ni coating effectively improved the discharge capacity, but decreased the cycling performance of the as-synthesized Ni-coated Mg2Ni alloys. The discharge current has a great impact on the cycling performance of the as-synthesized Ni-coated Mg2Ni alloys.     

Structural and electrochemical hydrogen storage properties of Mg2Ni-based alloys

Four different methods, i.e. hydriding combustion synthesis + mechanical milling (HCS + MM), induction melting (followed by hydriding) + mechanical milling (IM(Hyd) + MM), combustion synthesis + mechanical milling (CS + MM) and induction melting + mechanical milling (IM + MM), were used to prepare Mg₂Ni-based hydrogen storage alloys used as the negative electrode material in a nickel-metal hydride (Ni/MH) battery. The structural and electrochemical hydrogen storage properties of the Mg₂Ni-based alloys have been investigated systematically. The XRD results indicate that the as-milled products show nanocrystalline or amorphous-like structures. Electrochemical measurements show that the as-milled hydrides exhibit higher discharge capacity and better electrochemical kinetic property than the as-milled alloys. Among the four different methods, the HCS + MM product possesses the highest discharge capacity (578 mAh g⁻¹), the best high rate dischargeability (HRD) and the highest exchange current density (58.8 mA g⁻¹). It is suggested that the novel method of HCS + MM is promising to prepare Mg-based hydrogen storage electrode alloy with high discharge capacity and activity.     

Effect of commercial AB5 alloy addition on the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys

A commercial AB5 hydrogen storage alloy was used as an additive to improve the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys.The effect of AB5 alloy addition on the phase structure,charge/discharge characteristics,and electrochemical kinetics of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy was investigated.The maximum discharge capacity of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 + 4 wt.% AB5 electrode reaches 406 mAh/g.The anodic polarization,cyclic voltammetry,and potential step discharge experiments show that the electrochemical kinetics of the electrode with additives was promoted,with the LaNi5 phase of AB5 alloy acting as electro-catalytic sites in the electrode alloy.The high-rate dischargeability of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 + 4 wt.% AB5 alloy electrode at 1100 mA/g reaches 60.9%,which is 9.4% higher than that of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy electrode.The cycling stability of the electrode with 4 wt.% AB5 alloy has also been improved.     

La–Mg–Ni ternary hydrogen storage alloys with Ce2Ni7-type and Gd2Co7-type structure as negative electrodes for Ni/Mh batteries

Hydrogen strorage alloys with formula La_1.5Mg_0.5Ni₇ were prepared by induction melting followed by different annealing treatments (1073, 1123 and 1173 K) for 24 h. The alloy composition, alloy microstructure and electrochemical properties were investigated, respectively. The results showed that the multi-phase structure of as-cast alloy was converted into a double-phase structure (Gd₂Co₇-type phase and Ce₂Ni₇-type phase) through annealing treatments. Mg atoms were mainly located in Laves unit of Gd₂Co₇-type unit cell and Ce₂Ni₇-type unit cell. The electrochemical capacity of alloy electrodes after annealing treatment could be up to 390 mAh/g. The cyclic stability of alloy electrodes was significantly improved by annealing treatments; After 150 charge/discharge cycles, the capacity retention ratio of alloy annealed at 1173 K was the highest (81.9%). The high rate dischargeability of alloy electrodes was also improved due to annealing treatment.     

Electrochemical hydrogen storage properties of non-stoichiometric La0.7Mg0.3−xCaxNi2.8Co0.5 (x = 0-0.10) electrode alloys

The microstructure and electrochemical hydrogen storage characteristics of La_0.7Mg_0.3−xCa_xNi_2.8Co_0.5 (x = 0, 0.05 and 0.10) alloys prepared by arc-melting and subsequent powder sintering method are investigated. The electrochemical measurement results show that the cycle stability after 100 charge/discharge cycles first increases from 46.4% (x = 0) to 54.3% (x = 0.05), then decreases to 43.2% (x = 0.10), and the high rate dischargeability increases from 64.5% (x = 0) to 68.5% (x = 0.10) at the discharge current density of 1200 mA/g. The electrochemical impedance spectroscopy analysis indicates that the electrochemical kinetics of the alloy electrodes is improved by increasing Ca. The entire results exhibit that a suitable content of Ca (x = 0.05) can improve the overall electrochemical hydrogen storage characteristics of the alloys.     

Effect of alloy composition on enthalpy and entropy changes of hydride formation for stoichiometric and nonstoichiometric hydrogen storage alloys

Both enthalpy change ΔH° and entropy change ΔS° of hydride formation were evaluated from the measurement of pressure-composition isotherms (P-C-T curves) for hydrogen desorption in stoichiometric and nostoichiometric Mm (Ni₁₆Mn_11.4Al_0.3Co_0.7)₃ (Mm = misch metal, 0.88 x 1.12 values decreased with increasing x value, supporting that the low stability of the hydride causes the improved high-rate dischargeability of the Mm-poor Mm(Ni₁₆Mn_0.4Al_0.3Co_0.7)₁₁₂ alloy electrode.     

Effects of B, Fe, Gd, Mg, and C on the structure, hydrogen storage, and electrochemical properties of vanadium-free AB2 metal hydride alloy

The structural, gaseous phase hydrogen storage, and electrochemical properties of a series of vanadium-free AB₂ Laves phase based metal hydride alloys with various modifiers (Ti₅Zr₃₀Cr₉Mn₁₉Co₅Ni_32−xM_x, M = B, Fe, Gd, Mg, and C) were studied. While B and Fe completely dissolve in the main AB₂ phases, Gd, Mg, and C form individual secondary phases. The solubilities of Gd, Mg, and C in the AB₂ phases are not detectable, 0.3 at.%, and very low, respectively. The C14 crystallite sizes, C15 phase abundances, and Zr₇Ni₁₀ phase abundances of modified alloys are larger than those of the base alloy. All modified alloys show decreases in plateau pressure, reversible gaseous phase storage capacity, formation activity, electrochemical capacity, and cycle life. A small amount of boron (0.2 at.%) and carbon in the alloy improve the half-cell high-rate dischargeability and bulk hydrogen diffusion. All modifiers, except for boron, reduce the surface exchange reaction current densities of the alloys. Both Mg and C show improvement in charge retention. Full-cell high-rate performance is improved by adding only a small amount of boron (0.2 at.%). Fe, Gd and 0.2 at.% of boron improve the low-temperature performance of the sealed batteries.