In order to improve the hydrogenation and dehydrogenation performances of the Mg2Ni-type alloys, Mg was partially substituted by La in the alloy, and melt spinning technology was used for the preparation of the Mg20-xLaxNi10 （x=0, 2, 4, 6） hydrogen storage alloys. The structures of the alloys were studied by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and high-resolution transmission electron microscopy （HRTEM）. It was found that no amorphous phase formed in the as-spun La-free alloy, but the as-spun alloys containing La held a major amorphous phase. When La content x≤2, the major phase in the as-cast alloys was Mg2Ni phase, but with further increase of La content, the major phase of the as-cast alloys changed into LaNi5＋LaMg3 phase. Thermal stability of the as-spun alloys was studied by differential scanning calorimetry （DSC）, showing that spinning rate was a negligible factor on the crystallization temperature of the amorphous phase. The hydrogen absorption and desorption kinetics of the as-cast and as-spun alloys were measured using an automatically controlled Sieverts apparatus, confirming that the hydrogen absorption and desorption capacities and kinetics of the as-cast alloys clearly increased with rising La content. For La content x=2, the as-spun alloy displayed optimal hydrogen desorption kinetics at 200 ℃.
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.
The La-Mg-Ni system A2B7-type electrode alloys with nominal composition La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1(x=0,0.05, 0.1,0.15,0.2)were prepared by casting and melt-spinning.The influences of melt spinning on the electrochemical performances as well as the structures of the alloys were investigated.The results obtained by XRD,SEM and TEM show that the as-cast and spun alloys have a multiphase structure,consisting of two main phases(La,Mg)Ni3 and LaNi5 as well as a residual phase LaNi2.The melt spinning leads to an obvious increase of the LaNi5 phase and a decrease of the(La,Mg)Ni3 phase in the alloys.The results of the electrochemical measurement indicate that the discharge capacity of the alloys(x≤0.1)first increases and then decreases with the increase of spinning rate,whereas for x>0.1,the discharge capacity of the alloys monotonously falls.The melt spinning slightly impairs the activation capability of the alloys,but it significantly enhances the cycle stability of the alloys.
The nanocrystalline and amorphous Mg2Ni-type Mg2- xLaxNi （x=0, 0.2） hydrogen storage alloys were synthesized by melt-spinning technique. The as-spun alloy ribbons were obtained. The microstructures of the as-spun ribbons were characterized by X-ray diffraction （XRD）, high resolution transmission electronic microscopy （HRTEM） and electron diffraction （ED）. The hydrogen absorption and desorption kinetics of the alloys were measured using an automatically controlled Sieverts apparatus, and their electrochemical kinetics were tested by an automatic galvanostatic system. The electrochemical impedance spectrums （EIS） were plotted by an electrochemical workstation （PARSTAT 2273）. The hydrogen diffusion coefficients in the alloys were calculated by virtue of potential-step method. The obtained results showed that no amorphous phase was detected in the as-spun La-free alloy, but the as-spun alloys substituted by La held a major amorphous phase, con- firming that the substitution of La for Mg markedly intensified the glass forming ability of the Mg2Ni-type alloy. The substitution of La for Mg notably improved the electrochemical hydrogen storage kinetics of the Mg2Ni-type alloy. Furthermore, the hydrogen storage kinetics of the experimental alloys was evidently ameliorated with the spinning rate growing.
The nanocrystalline and amorphous Mg2Ni-type alloys with nominal compositions of Mg2Ni1-xMnx （x=0, 0.1, 0.2, 0.3, 0.4） were synthesized by melt-spinning technique. The spun alloy ribbons with a continuous length, a thickness of about 30 μm and a width of about 25 mm are obtained. The structures of the as-spun alloy ribbons were characterized by XRD and HRTEM. The electrochemical hydrogen storage characteristics of the as-spun alloy ribbons were measured by an automatic galvanostatic system. The electrochemical impedance spectrums （EIS） were plotted by an electrochemical workstation. The hydrogen diffusion coefficients （D） in the alloys were calculated by virtue of potential-step measurement. The results show that all the as-spun （x=0） alloys hold a typical nanocrystalline structure, whereas the as-spun （x=0.4） alloy displays a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni facilitates the glass formation in the Mg2Ni-type alloy. The substitution of Mn for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, involving the discharge capacity and the electrochemical cycle stability. With an increase in the amount of Mn substitution from 0 to 0.4, the discharge capacity of the as-spun （20 m/s） alloy increases from 96.5 to 265.3 mA·h/g, and its capacity retaining rate （S20） at the 20th cycle increases from 31.3% to 70.2%. Furthermore, the high rate dischargeability （HRD）, electrochemical impedance spectrum and potential-step measurements all indicate that the electrochemical kinetics of the alloy electrodes first increases then decreases with raising the amount of Mn substitution.
In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of the AB3.5-4.1-type electrode alloys, the La-Mg-Ni-Co system La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x= 0, 0.2, 0.4, 0.6) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The results show that the structures and electrochemical performances of the alloys are closely relevant to the B/A ratio. All the alloys exhibit a multiphase structure, including two major phases, (La, Mg)2Ni7 and LaNi5, and a residual phase LaNi2, and with rising ratio B/A, the (La,Mg)2Ni7 phase decreases and the LaNi5 phase increases significantly. When ratio B/A=3.7, the alloys obtain the maximum discharge capacities. The high rate discharge(HRD) capability of the alloy (M=Ni) monotonously rises with growing B/A ratio, but that of the alloy (M=Co) first mounts up then declines. The cycle stability of the alloy (M=Co) monotonously increases with rising B/A ratio, but it first decreases slightly then increases for the alloy (M=Ni). The discharge potential of the alloy (M=Ni) declines with increasing B/A ratio (x>0.2), but for the alloy (M=Co), the result is contrary. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed ratio B/A=3.7, the Co substitution enhances the discharge capacity from 365.7 to 401.8 mA·h/g, the capacity retention ratio (S100) after 100 charging-discharging cycles from 50.32% to 53.26% and the HRD from 88.65% to 90.69%.
The Mg2Ni-type alloys with nominal compositions of Mg20Ni10-xCox(x=0,1,2,3,4,%,mass fraction) were prepared by melt-spinning technology.The structures of the alloys were studied by XRD,SEM and HRTEM.The hydrogen absorption/desorption kinetics and the electrochemical performances of the alloys were measured.The results show that no amorphous phase forms in the as-spun Co-free alloy,but the as-spun alloys containing Co show a certain amount of amorphous phase.The hydrogen absorption capacities of the as-cast alloys first increase and then decrease with the incremental change of Co content.The hydrogen desorption capacities of as-cast and spun alloys rise with increasing Co content.The melt spinning significantly improves the hydrogenation and dehydrogenation capacities and kinetics of the alloys.The substitution of Co for Ni clearly enhances the discharge capacities of the alloys and the cycle stability of the as-spun alloys.
