In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 （x=0, 0.1, 0.2, 0.3, 0.4） elec-trode alloys were fabricated by casting and annealing. The microstructures of the as-cast and annealed alloys were characterized by XRD and SEM. The electrochemical hydrogen storage characteristics of the as-cast and annealed alloys were measured. The results revealed that all of the experimental alloys mainly consisted of two phases： （La,Mg）2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. As Sm content grew from 0 to 0.4, the discharge capacity and the high rate discharge ability （HRD） first in-creased and then decreased for the as-cast and annealed alloys, whereas the capacity retaining rate （S100） after 100 cycles increased continuously.
In this paper, we comprehensively investigate the influences of M（M=Cu, Co, Mn） substitution for Ni on the structures and electrochemical hydrogen storage characteristics of the nanocrystalline and amorphous Mg20Ni10-xMx（M=Cu, Co, Mn; x = 0–4） alloys prepared by melt spinning. The as-spun（M=None, Cu） alloys display an entire nanocrystalline structure, whereas the as-spun（M=Co, Mn） alloys hold a mixed structure of both nanocrystalline and amorphous when x = 4（M content）. These results indicate that the substitution of M（M=Co, Mn） for Ni facilitates the glass formation in Mg2Ni-type alloy. All the as-spun alloys have the Mg2 Ni major phase, but M（M=Co, Mn） substitution brings on some secondary phases,such as Mg Co2, Mg phases for M=Co, and Mn Ni, Mg phases for M=Mn. The substitution of M（M=Cu, Co, Mn）for Ni also makes a positive contribution to the cycle stability of the alloys in the following orders：（M=Cu） [（M=Co） [（M=Mn） for x = 1 and（M=Co） [（M=Mn）[（M=Cu） for x = 2–4. Meanwhile, it notably enhances the discharge capacity of the alloys in the sequence of（M=Co） [（M=Mn） [（M=Cu）. As for the high rate discharge ability, it visibly upgrades with the growing of M content for（M=Cu, Co）, while it grows at first and then declines for（M=Mn）.
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.
ZHANG Yanghuan YANG Tai CAI Ying HOU Zhonghui REN Huiping ZHAO Dongliang
In order to improve the electrochemical hydrogen storage performance of the Mg2Ni-type electrode alloys, Mg in the alloy was partially substituted by La, and the nanocrystalline and amorphous Mg2Ni-type Mg20-xLaxNi10 （x-=0, 2） alloys were synthesized by melt-spinning technique. The microstructures of the as-spun alloys were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and transmission electron microscopy （TEM）. The electrochemical hydrogen storage properties of the experimental alloys were tested. The results show that no amorphous phase is detected in the as-spun Mg20Ni10 alloy, but the as-spun Mg18La2Ni10 alloy holds a major amorphous phase. As La content increases from 0 to 2, the maximum discharge capacity of the as-spun （20 m/s） alloys rises from 96.5 to 387.1 mA.h/g, and the capacity retaining rate （S20） at the 20th cycle grows from 31.3% to 71.7%. Melt-spinning engenders an impactful effect on the electrochemical hydrogen storage performances of the alloys. With the increase in the spinning rate from 0 to 30 m/s, the maximum discharge capacity increases from 30.3 to 135.5 mA.h/g for the Mg20Ni10 alloy, and from 197.2 to 406.5 mA-h/g for the Mg18La2Ni10 alloy. The capacity retaining rate （S20） of the Mg2oNi10 alloy at the 20th cycle slightly falls from 36.7% to 27.1%, but it markedly mounts up from 37.3% to 78.3% for the Mg18La2Ni10 alloy.
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.
