Structures and hydrogen storage properties of RE-Mg-Ni-Mn-based AB2-type alloys prepared by casting and melt spinning

To ameliorate the electrochemical hydrogen storage properties of RE-Mg-Ni-Mn-based AB2-type electrode alloys,La element was partially substituted by Ce,and La1-xCexMgNi3.5Mn0.5(x=0,0.1,0.2,0.3,0.4)alloys were fabricated by casting and melt spinning.The effects of Ce content on structures and electrochemical hydrogen storage properties of prepared alloys were studied in detail.Results show that the experimental alloys consist of LaMgNi4 and LaNi5 phases.The variation of Ce content,instead of changing phase composition,results in an obvious phase abundance change in the alloys,namely the amount of LaMgNi4 and LaNi5 phases,respectively,increases and decreases with Ce content growing.Moreover,the partial substitution of Ce for La leads to that the lattice keeps constant,cell volumes clearly decreases and the alloy grains are markedly refined.The electrochemical measurements reveal that the as-cast and as-spun alloys obtain the maximum discharge capacities at the first cycling without any activation needed.With Ce content increasing,the discharge capacity of as-cast alloys visibly decreases.By contrast,the as-spun alloys have the maximum discharge capacity value.The substitution of Ce for La dramatically promotes the cycle stability.Moreover,the electrochemical kinetic performances of as-cast and asspun alloys first increase and then decrease with Ce content increasing.

Electrochemical hydrogen storage behaviors of as-cast and spun RE-Mg-Ni-Co-Al-based AB2-type alloys applied to Ni-MH battery

Preparation of La-Mg-Ni-Co-Al-based AB2-type alloys La0.8-xCe0.2YxMgNi3.4Co0.4Al0.1(x=0,0.05,0.10,0.15,0.20)was performed using melt spinning technology.The influences of spun rate and Y content on structures and electrochemical hydrogen storage characteristics were studied.The base phase LaMgNi4 and the lesser phase LaNis were detected by X-ray diffraction(XRD)and scanning electron microscope(SEM).The variations of spinning rate and Y content cause an obvious change in phase content,but without altering phase composition,namely,with spinning rate and Y content growing,LaMgNi4 phase content augments while LaNi5 content declines.Furthermore,melt spinning and the replacing La by Y refine the grains dramatically.The electrochemical tests show a favorable activation capability of the two kinds of alloys,and the maximum discharge capacities are achieved during the first cycle.Discharge capacity firstly increases and subsequently decreases with spinning rate rising,while cycle stability is ameliorated and discharge capacity decreases with Y addition increasing.It is found that the amelioration of cycle stability is due to the enhancement of anti-pulverization,anti-corrosion and antioxidation abilities by both replacement of La with Y and melt spinning.Moreover,with the increase of Y addition and/or spinning rate,the electrochemical kinetics that contain charge transfer rate,limiting current density(IL),hydrogen diffusion coefficient(D)and the high rate discharge ability(HRD)firstly augment and then reduce.

Structures and electrochemical hydrogen storage performance of Si added A_2B_7-type alloy electrodes

In order to ameliorate the electrochemical hydrogen storage performance of La-Mg-Ni system A2B7-type electrode alloys, a small amount of Si was added. The La0.8Mg0.2Ni3.3Co0.2Six （x=0-0.2） electrode alloys were prepared by casting and annealing. The effects of adding Si on the structure and electrochemical hydrogen storage characteristics of the alloys were investigated systematically. The results indicate that the as-cast and annealed alloys hold multiple structures, involving two major phases of （La, Mg）2Ni7 with a Ce2Ni7-type hexagonal structure and LaNi5 with a CaCu5-type hexagonal structure as well as one residual phase LaNi3. The addition of Si results in a decrease in （La, Mg）2Ni7 phase and an increase in LaNi5 phase without changing the phase structure of the alloys. What is more, it brings on an obvious effect on electrochemical hydrogen storage characteristics of the alloys. The discharge capacities of the as-cast and annealed alloys decline with the increase of Si content, but their cycle stabilities clearly grow under the same condition. Furthermore, the measurements of the high rate discharge ability, the limiting current density, hydrogen diffusion coefficient as well as electrochemical impedance spectra all indicate that the electrochemical kinetic properties of the electrode alloys first increase and then decrease with the rising of Si content.

Electrochemical Hydrogen Storage Performances of the Si Added La-Mg-Ni-based A_2B_7-type Electrode Alloys for Ni/MH Battery Application

The casting and annealing technologies were applied to fabricate the La0.8Mg0.2Ni3.3Co0.2Six （x = 0-0.2） electrode alloys. The effects of Si content and annealing temperature on the structure and electrochemical performances of the alloys were investigated systematically. The analyses of XRD and SEM show that all the alloys possess a multiphase structure, involving two main phases （La, Mg）2Ni7 and LaNi5 as well as a residual phase LaNi3. The addition of Si brings on an evident increase in the LaNi5 phase and a decrease in the （La, Mg）2Ni7 phase, without altering the main phase component of the alloy, which also makes the lattice constants and cell volumes of the alloy enlarged. Likewise, the annealing treatment engenders the same action on the lattice constants and cell volumes as adding Si. Simultaneously, it gives rise to the variation of the phase abundance and the coarsening of the alloy grains. The electrochemical measurements indicate that the addition of Si ameliorates the cycle stability of the as-cast and annealed alloys significantly, but impairs their discharge capacities clearly. Similarly, the annealing treatment makes a positive contribution to the cycle stability of the alloy evidently, and the discharge capacity of the alloy shows a maximum value with annealing temperature rising. Furthermore, the high rate discharge ability （HR） first augments and then declines with the rising of Si content and annealing temperature.

Effect of cobalt content on electrochemical performance of La-Mg-Ni system (Ce_2Ni_7-type) electrode alloys

In order to improve the cyclic stability of La-Mg-Ni system （Ce2Ni7-type） alloy electrode, small amount of Co was added in La0.75Mg0.25Ni3.5 alloy. The effect of Co on electrochemical performance and microstructure of the alloys were investigated in detail. XRD results showed that the alloys had multiphase structure composed of （La, Mg）2Ni7, LaNi5 and small amount of LaNi2 phases. The discharge capacity of the alloys first increased and then decreased with increasing Co content. At a discharge current density of 900 mA/g, the HRD of the alloy electrodes increased from 81.3% （x=0） to 89.2 % （x=0.2）, and then reduced to 87.8 % （x=0.6）. After 60 charge/discharge cycles, the capacity retention rate of the alloys enhanced from 52.67% to 61.32%, and the capacity decay rate of the alloys decreased from 2.60 to 2.05 mAh/g per cycle with increasing Co content. The obtained results by XPS and XRD showed that the fundamental reasons for the capacity decay of the La-Mg-Ni system （Ce2Ni7-type） alloy electrodes were corrosion and oxidation as well as passivation of Mg and Lain alkaline solution.

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

Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is great, resulting in a linear decrease of the unit cell parameters of main phases and increase of hydrogen absorption/desorption plateau as Mg content increases. Electrochemical measurements show that as the Mg content increases, the discharge capacity of alloy electrodes first increases and then decreases. The cyclic stability presents a deteriorative trend. La1.4Mg0.6 Ni7 alloy electrode exhibits the maximum electrochemical discharge capacity （378 mAh·g^-1）, and the La1.6Mg0.4Ni7 alloy electrode shows the best cyclic stability （S270 = 81%）.

Effect of electroless plating nickel treatment on electrode properties of Zr-based AB_2 type alloy

An electroless plating nickel treatment was processed to improve the active behaviors and discharge capacities of Zr based AB 2 alloys. The effects of the nickel coating on the surface appearance, the structure of the alloy powders and the electrode characteristics were investigated. It is found that the Ni rich layer formed through electroless plating nickel treatment plays an important role on the initial activation property and the discharge capacity of Zr based alloy. The optimal content of electroless plating nickel is about 15%, and the discharge capacity of the electrode can be increased to 400?mA·h·g -1 after 6 cycles. Although coated nickel is beneficial for quick activation and discharge capacity, excessive electroless plating nickel can result in a decreased discharge capacity.

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.

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%.

Effects of alloying side B on Ti-based AB_2 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 nickel-metal 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 performances are 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.

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.

Impacts of Melt Spinning and Element Substitution on Electrochemical Characteristics of the La–Mg–Ni-based A₂B₇-Type Alloys

The partial substitution of Zr for La has been performed in order to ameliorate the electrochemical hydrogen storage performances of La–Mg–Ni based A2B7-type electrode alloys. The melt spinning technology was used to prepare the La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1 (x=0, 0.05, 0.1, 0.15, 0.2) electrode alloys. The impacts of the melt spinning and the substituting La with Zr on the structures and the electrochemical hydrogen storage characteristics of the alloys were systemically investigated. The analysis of XRD and TEM reveals that the as-cast and spun alloys have a multiphase structure, composing of two main phases (La, Mg)2Ni7 and LaNi5 as well as a residual phase LaNi2. The electrochemical measurement indicates that both the substitution of Zr for La and the melt spinning ameliorate the electrochemical cycle stability of the alloys dramatically. Furthermore, the high rate discharge ability (HRD) of the as-spun (10 m/s) alloys notably declines with growing the amount of Zr substitution, while it first augments and then falls for the (x=0.1) alloy with rising the spinning rate.

Electrochemical hydrogen storage characteristics of as-cast and annealed La_(0.8-x)Nd_xMg_(0.2)Ni_(3.15)Co_(0.2)Al_(0.1)Si_(0.05)(x=0-0.4)alloys

The La-Mg-Ni-based A2B7-type La0.8-xNdxMg0.2Ni3.15Co0.2Al0.15 （x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were prepared by casting and annealing. The influences of partial substitution of Nd for La on the structure and electrochemical performance of the as-cast and annealed alloys were investigated. It was found that the experimental alloys consist of two major phases, （La, Mg）2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure, as well as some residual phase LaNi3 and NdNi5. The discharge capacity and high rate discharge ability （HRD） of the as-cast and annealed alloys first increase and then decrease with Nd content growing. The as-cast and annealed alloys （x=0.3） yield the largest discharge capacities of 380.3 and 384.3 mA·h/g, respectively. The electrochemical cycle stability of the as-cast and annealed alloys markedly grows with Nd content rising. As the Nd content increase from 0 to 0.4. The capacity retaining rate （S100） at the 100th charging and discharging cycle increases from 64.98% to 85.17% for the as-cast alloy, and from 76.60% to 96.84% for the as-annealed alloy.

熔体快淬对AB_2型Laves相储氢电极合金循环寿命的影响

研究了快淬处理对 AB2 型 Laves 相电极合金循环稳定性的影响,用 XRD 和 SEM 分析了铸态及快淬态合金的相结构,并观察了合金的微观组织形貌。结果表明,快淬对 AB2 型贮氢合金循环稳定性的影响与合金的成分密切相关。快淬对 Ti 基电极合金的循环寿命有所提高,但不显著;对 Ti-Zr 基合金,随淬速增加,合金的循环稳定性急剧增加。快淬使 AB2 型电极合金循环寿命发生变化的根本原因是合金中形成了不同量的非晶相。

热处理对 AB_2 型合金 MH-Ni 电池寿命的影响

对以ＡＢ２型合金为负极的ＭＨ－Ｎｉ电池的寿命进行了系统研究。采用封口化成工艺、负极为ＡＢ２型合金的ＭＨ－Ｎｉ电池在活化初期及大倍率充电时，由于ＡＢ２型合金较ＡＢ５型合金难活化及动力学性能差，内压更易升高，造成电池喷爬碱和微漏气，电池寿命变短。负极为ＡＢ２型合金的电池经过热处理，可显著改善电池寿命特性，为ＡＢ２型合金在ＭＨ－Ｎｉ电池中的应用提供了重要条件。

A_(2)B_(7)-type La-Mg-Ni alloys prepared by Mg thermal diffusion for improved hydrogen storage performance

A novel approach based on thermal diffusion was used to achieve controllable Mg content in A_(2)B_(7)-type La-Mg-Ni-based alloys.The formation mechanism of the A_(2)B_(7)-type phase as a result of the thermal diffusion process and the effect of Mg content on hydrogen storage performance were investigated.X-ray diffraction(XRD)patterns and Rietveld refinement results showed that increased Mg transformed the LaNi_(5)phase in the La_(0.74)Sm_(0.03)Y_(0.23)Ni_(4.32)Al_(0.04)precursor alloy into a superlattice structure.Scanning electron microscopy(SEM)images showed that Mg was evenly distributed in the alloy bulk.Mg in the superlattice significantly inhibited the phase decomposition of the superlattice structure during the hydrogen absorption/desorption cycles.An A_(2)B_(7)-type La_(0.57)Sm_(0.02)Y_(0.18)Mg_(0.23)Ni_(3.38)Al_(0.03)alloy composed of Gd_(2)Co_(7)and Ce_(2)Ni_(7)phases was successfully synthesized.The pressure-composition isotherm profiles showed that the alloy had a hydrogen storage capacity as high as 1.73 wt%,with good cycling stability.After 50 cycles of hydrogen absorption/desorption,the alloy retained a hydrogen storage capacity of 1.45 wt%,with a capacity retention rate of up to 84.28%.The Mg thermal diffusion process thus provides a new approach for the controlled preparation of La-Mg-Ni-based alloys.

Compositional tuning of A_(2)B_(7)-type La_(0.7-x)Y_(x)Mg_(0.3)Ni_(3.5)alloys for gaseous hydrogen storage

Rare earth-based superlattice alloys have great potential for gaseous hydrogen storage,as well as successful application as nickel-metal hydride batteries anodes.In this work,Y substitution was carried out to adjust the gaseous hydrogen storage properties of A_(2)B_(7)-type La_(0.7)Mg_(0.3)Ni_(3.5)alloys.The results indicate a multiphase structure in the alloys comprised of the main rhombohedral Gd_(2)Co_(7)and PuNi_(3)phases,with a small amount of CaCu_(5)phase.Moreover,the Y substitution results in higher abundance of the Gd_(2)Co_(7)phase.The alloy La_(0.42)Y_(0.28)Mg_(0.3)Ni_(3.5)exhibits a hydrogen storage cap acity of 1.55 wt%at 298 K and a desorption plateau pressure of 0.244 MPa.In addition,this alloy demonstrates a stable cycle life by a capacity retention of 94.2%after 50 cycles,with the main capacity degradation occurring during the initial 20 cycles.This work accentuates the potential of the La-Y-Mg-Ni-based superlattice alloys for applications in solid-state hydrogen storage.

Effect of annealing temperature on microstructure and electrochemical performance of La_(0.75)Mg_(0.25)Ni_(3.5)Co_(0.2) hydrogen storage electrode alloy

To improve the cyclic stability of La-Mg-Ni system alloy, as-cast La0.75Mg0.25Ni3.5Co0.2 alloy was annealed at 1123, 1223, and 1323 K for 10 h in 0.3 MPa argon. The microstructure and electrochemical performance of different annealed alloys were investigated systematically by X-Ray Diffraction （XRD）, Scanning Electron Microscopy （SEM）, X-Ray Photoelectron Spectroscopy （XPS）, and electrochemical experiments. The results obtained by XRD and SEM showed that the as-cast and annealed （1123 K） alloys had multiphase structure containing LaNis, （La, Mg）2（Ni, Co）7 and few LaNi2 phases. When annealing temperatures approached 1223 and 1323 K, LaNi2 phase disappeared. The annealed alloys at 1223 and 1323 K were composed of LaNi5, （La, Mg）2（Ni, Co）7 and （La, Mg）（Ni, Co）3 phases. With increasing annealing temperature, the maximum discharge capacity of the alloy decreased monotonously, but the cyclic stability was improved owing to structure homogeneity and grain growth after annealing, as well as the enhancement of anti-oxidation/corrosion ability and the suppression of pulverization during cycling in KOH electrolyte.

Electrochemical performances of as-cast and annealed La_(0.8-x)Nd_xMg_(0.2)Ni_(3.35)Al_(0.1)Si_0.05(x=0-0.4) alloys applied to Ni/metal hydride (MH) battery

The La-Mg-Ni-based A2B7-type Lao.8_xNdx Mgo.2Ni3.35Alo.lSio.o5 （x = 0, 0.1, 0.2, 0.3, and 0.4） electrode alloys were prepared by casting and annealing. The influence of the partial substitution of Nd for La on the structure and electrochemical performances of the alloys was investigated. The structural analysis of X-ray diffraction and scanning electron microscopy reveals that the experimental alloys consist of two major phases： （La,Mg）2Ni7 with the hexagonal Ce2Ni7-type structure and LaNi5 with the hexagonal CaCus-type structure as well as some residual phases of LaNi3 and NdNis. The electrochemical measurements indicate that an evident change of the electrochemical performance of the alloys is associated with the substitution of Nd for La. The discharge capacity of the alloy first increases then decreases with the growing Nd content, whereas their cycle stability clearly grows all the time. Furthermore, the measurements of the high rate discharge ability, the limiting current density, and hydrogen diffusion coefficient all demonstrate that the electrochemical kinetic properties of the alloy electrodes first augment then decline with the rising amount of Nd substitution.

Electrochemical hydrogen storage characteristics of La_(0.75-x) M_xMg_(0.25)Ni_(3.2)Co_(0.2)Al_(0.1)(M=Zr,Pr;x=0,0.1) alloys prepared by melt spinning

In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology was used to fabricate the La_(0.75-x)M_xMg_0.25Ni_3.2Co_0.2Al_0.1 (M = Zr, Pr; x = 0, 0.1) electrode alloys. The influences of the melt spinning and substituting La with M (M = Zr, Pr) on the structures and the electrochemical hydrogen storage characteristics of the alloys were investigated. The analysis of XRD, SEM, and TEM reveals that the as-cast and spun alloys have a multiphase structure composed of two main phases (La, Mg)_2Ni_7 and LaNi_5 as well as a residual phase LaNi_2 . The as-spun (M = Pr) alloy displays an entire nanocrystalline structure, while an amorphous-like structure is detected in the as-spun (M = Zr) alloy, implying that the substitution of Zr for La facilitates the amorphous formation. The electrochemical measurements exhibit that the substitution of Pr for La clearly increases the discharge capacity of the alloys; however, the Zr substitution brings on an adverse impact. Meanwhile, the M (M = Zr, Pr) substitution significantly enhances its cycle stability. The melt spinning exerts an evident effect on the electrochemical performances of the alloys, whose discharge capacity and high rate discharge ability (HRD) first mount up and then fall with the growing spinning rate, whereas their cycle stabilities monotonously augment as the spinning rate increases.