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.
The nanocrystalline and amorphous LaMg11Ni ＋ x wt% Ni （x = 100, 200） composites were synthesized by the mechanical milling, and their gaseous and electrochemical hydrogen storage kinetics performance were systematically investigated, The results indicate that the as-milled composites exhibit excellent hydrogen storage kinetic performances, and increasing Ni content significantly facilitates the improvement of the hydrogen storage kinetics properties of the composites. The gaseous and electrochemical hydrogen storage kinetics of the composites reaches a maximum value with the variation of milling time. Increasing Ni content and milling time both make the hydrogen desorption activation energy lower, which are responsible for the enhancement in the hydrogen storage kinetics properties of the composites. The diffusion coefficient of hydrogen atom and activation enthalpy of charge transfer on the surface of the as-milled composites were also calculated, which are considered to be the dominated factors for the electrochemical high rate discharge ability.
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
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.
In order to improve the gaseous and electrochemical hydrogen storage kinetics of the M2Nitype alloy, the elements Cu and Nd were added in the alloy. The nanocrystalline and amorphous Mg2Ni-type alloys with the composition of（Mg24Ni10Cu2）100-xNdx（x = 0, 5, 10, 15, 20） were prepared by melt spinning technology. The effects of Nd content on the structures and hydrogen storage kinetics of the alloys were investigated. The characterization by X-ray diffraction（XRD）, transmission electron microscopy（TEM） and scanning electron microscopy（SEM） reveals that all the as-cast alloys hold multiphase structures, containing Mg2Ni-type major phase as well as some secondary phases Mg6Ni, Nd5Mg41, and Nd Ni, whose amounts clearly grow with increasing Nd content. Furthermore, the as-spun Nd-free alloy displays an entire nanocrystalline structure, whereas the as-spun Nd-added alloys hold a mixed structure of nanocrystalline and amorphous structure and the amorphization degree of the alloys visibly increases with the rising of the Nd content, suggesting that the addition of Nd facilitates the glass forming in the Mg2Ni-type alloy. The measurement of the hydrogen storage kinetics indicates that the addition of Nd significantly improves the gaseous and electrochemical hydrogen storage kinetics of the alloys. The addition of Nd enhances the diffusion ability of hydrogen atoms in the alloy, but it impairs the charge-transfer reaction on the surface of the alloy electrode, which makes the high rate discharge ability（HRD） of the alloy electrode fi rst mount up and then go down with the growing of Nd content.
The nanocrystalline and amorphous Mg-Nd-Ni-Cu quaternary alloys with a composition of （Mg24Ni10Cu2）loo-xNdx （x = 0-20） were prepared by melt spinning. The X-ray diffraction and transmission electron microscopy inspections reveal that, by varying the spinning rate and the Nd content, different microstructures could be obtained by melt spinning. Particularly, the as-spun Nd-free alloy holds an entire nanocrystalline structure but the as-spun Nd-added alloy has a nanocrystalline and amorphous structure, which implies that the addition of Nd facilitates the glass forming in the Mg2Ni-type alloy. Also, the degree of the amorphization in the as-spun Nd-added alloys clearly increases with increasing the spinning rate and the Nd content. The H-storage capacity and the hydrogenation kinetics of amorphous, partially and completely nanocrystalline alloys were investigated and it was found that they are dependent on the microstructure and the phase composition of the alloys. Specially, enhancing the spinning rate from 0 （the as-cast was defined as the spinning rate of 0 m/s） to 40 m/s makes the hydrogen absorption saturation ratio （R5a） （a ratio of the hydrogen absorption quantity in 5 min to the saturated hydrogen absorption capacity） increase from 35.2% to 90.3% and the hydrogen desorption ratio （R10d） （a ratio of the hydrogen desorption quantity in 10 min to the saturated hydrogen absorption capacity） rise from 12.7% to 44.9% for the （x = 5） alloy. And the growing of the Nd content from 0 to 20 gives rise to the R5a and R10d values rising from 85.7% to 94.5% and from 36.7% to 54.8% for the as-spun （30 m/s） alloys, respectively.
In order to examine the effects of structure stability on the degradation behaviors of multiphase La0.7Mg0.3Ni3 alloy,changes of the crystal structure and hydrogen storage properties after gas-solid cycling were investigated in detail.The structural analysis identifies that（La,Mg）Ni3（PuNi3-type） phase transforms to amorphous,i.e.,hydrogen-induced amorphization（HIA） occurs whereas LaNi5（CaCu5-type）,（La,Mg）2Ni7（Ce2Ni7-type）,and（La,Mg）5Ni19（Pr5Co19-type） phases still keep crystalline upon hydriding/dehydriding cycling.Partial amorphization remarkably affects both the gas-solid and electrochemical storage performances.The plateau of PCT curves becomes narrow and steep with cycling.Moreover,the maximum electrochemical capacity decreases notably after gas-solid hydrogenation repeats.The electrochemical capacity reduction could be ascribed to both drop of the maximum storage capacity and the slope of plateau induced by partial amorphization.For direct electrochemical cycling,it is suggested that the capacity decay is mainly attributed to HIA in the initial stage.
The element Ni in the Mg2Ni alloy is partially substituted by M（M = Cu, Co, Mn） in order to ameliorate the electrochemical hydrogen storage performances of Mg2Ni-type electrode alloys. The nanocrystalline and amorphous Mg20Ni10-xMx（M = None, Cu, Co, Mn; x = 0-4） alloys were prepared by melt spinning. The effects of the M（M = Cu, Co, Mn） content on the structures and electrochemical hydrogen storage characteristics of the as-cast and spun alloys were comparatively studied. The analyses by XRD, SEM and HRTEM reveal that all the as-cast alloys have a major phase of Mg2Ni but the M（M = Co, Mn） substitution brings on the formation of some secondary phases, MgCo2 and Mg for the（M = Co） alloy, and Mn Ni and Mg for the（M = Mn） alloy. Besides, the as-spun（M = None, Cu） alloys display an entirely nanocrystalline structure, whereas the as-spun（M = Co, Mn） alloys hold a nanocrystalline/amorphous structure, suggesting that the substitution of M（M = Co, Mn） for Ni facilitates the glass formation in the Mg2Ni-type alloys. The electrochemical measurements indicate that the variation of M（M = Cu, Co, Mn） content engenders an obvious effect on the electrochemical performances of the as-cast and spun alloys. To be specific, the cyclic stabilities of the alloys augment monotonously with increasing M（M = Cu, Co, Mn） content, and the capacity retaining rate（S20） is in an order of（M = Cu） 〉（M = Co） 〉（M = Mn） 〉（M = None） for x≤1 but changes to（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None） for x≥2. The discharge capacities of the as-cast and spun alloys always grow with the rising of M（M = Co, Mn） content but first mount up and then go down with increasing M（M = Cu） content. Whatever the M content is, the discharge capacities are in sequence：（M = Co） 〉（M = Mn） 〉（M = Cu） 〉（M = None）. The high rate discharge abilities（HRDs） of all the alloys grow clearly with rising M（M = Cu, Co） content except for（M = Mn） a
The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox （x = 0, 0.1, 0.2, 0.3, 0.4） alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo2 and Mg instead of altering the major phase Mg2Ni. No amorphous phase is detected in the as-quenched Co- ffee alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient （D） along with the limiting current density （IL） and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.
The as-cast RE-Mg-Ni-b ased AB2-type La1-xPrxMgNi3.6Co0.4(x=0-0.4)alloys were prepared by vacuum induction melting followed by annealing treatment.The phase composition and structure were characterized by X-ray diffraction(XRD)and scanning electron microscope(SEM).The results show that LaMgNi4 and LaNi5 coexist in as-cast alloys,but only LaMgNi4 is detected in the annealed alloys.The morphology of annealed alloys is more homogeneous than that of as-cast alloys.The gaseous hydrogen storage and electrochemical properties were investigated by pressure-composition isotherm(P-C-T)and electrochemical measurements.The P-C-T curves of annealed alloys show flatter and wider pressure plateaus corresponding to absorption/desorption pressure plateaus of LaMgNi4 hydride.But the maximum hydrogen storage content of annealed alloys is lower than that of as-cast alloys.In consideration of the electrochemical properties,the annealed La0.8Pr0.2MgNi3.6Co0.4alloy exhibits a maximum discharge capacity of354.2 mAh·g-1.
