Gaseous and Electrochemical Hydrogen Storage Kinetics of As-quenched Nanocrystalline and Amorphous Mg_2Ni-type Alloys

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.

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg12-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg_（12）-type LaMg_（11）Ni ＋ x wt% Ni（x = 100, 200） alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter（DSC） connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability（HRD） and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.

Improved Hydrogen Storage Kinetics of Nanocrystalline and Amorphous Mg-Nd-Ni-Cubased Mg_2Ni-type Alloys by Adding Nd

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.

Effect of ternary transition metal sulfide FeNi_(2)S_(4)on hydrogen storage performance of MgH_(2)

Hydrogen storage is a key link in hydrogen economy,where solid-state hydrogen storage is considered as the most promising approach because it can meet the requirement of high density and safety.Thereinto,magnesium-based materials(MgH_(2))are currently deemed as an attractive candidate due to the potentially high hydrogen storage density(7.6 wt%),however,the stable thermodynamics and slow kinetics limit the practical application.In this study,we design a ternary transition metal sulfide FeNi_(2)S_(4)with a hollow balloon structure as a catalyst of MgH_(2)to address the above issues by constructing a MgH_(2)/Mg_(2)NiH_(4)-MgS/Fe system.Notably,the dehydrogenation/hydrogenation of MgH_(2)has been significantly improved due to the synergistic catalysis of active species of Mg_(2)Ni/Mg_(2)NiH_(4),MgS and Fe originated from the MgH_(2)-FeNi_(2)S_(4)composite.The hydrogen absorption capacity of the MgH_(2)-FeNi_(2)S_(4)composite reaches to 4.02 wt%at 373 K for 1 h,a sharp contrast to the milled-MgH_(2)(0.67 wt%).In terms of dehydrogenation process,the initial dehydrogenation temperature of the composite is 80 K lower than that of the milled-MgH_(2),and the dehydrogenation activation energy decreases by 95.7 kJ·mol-1 compared with the milled-MgH_(2)(161.2 kJ·mol^(-1)).This method provides a new strategy for improving the dehydrogenation/hydrogenation performance of the MgH_(2)material.

An investigation of hydrogen storage kinetics of melt-spun nanocrystalline and amorphous Mg_2Ni-type 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.

Hydrogen Storage Kinetics of Nanocrystalline and Amorphous LaMg_(12)-Type Alloy–Ni Composites Synthesized by Mechanical Milling

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.

Catalytic effect comparison of TiO_(2) and La_(2)O_(3) on hydrogen storage thermodynamics and kinetics of the as-milled La-Sm-Mg-Ni-based alloy

In this investigation,mechanical grinding was applied to fabricating the Mg-based alloys La_(7)Sm_(3)Mg_(80)Ni_(10)+5 wt.%M(M=None,TiO_(2),La_(2)O_(3))(named La_(7)Sm_(3)Mg_(80)Ni_(10)-5 M(M=None,TiO_(2),La_(2)O_(3))).The result reveals that the structures of as-milled alloys consist of amorphous and nanocrystalline.The particle sizes of the added M(M=TiO_(2),La_(2)O_(3))alloys obviously diminish in comparison with the M=None specimen,suggesting that the catalysts TiO_(2)and La_(2)O_(3)can enhance the grinding efficiency.What’s more,the additives TiO_(2)and La_(2)O_(3)observably improve the activation performance and reaction kinetics of the composite.The time required by releasing 3 wt.%hydrogen at553,573 and 593 K is 988,553 and 419 s for the M=None sample,and 578,352 and 286 s for the M=TiO_(2)composite,and 594,366,301 s for the La_(2)O_(3)containing alloy,respectively.The absolute value of hydrogenation enthalpy change|△H|of the M(M=None,TiO_(2),La_(2)O_(3))alloys is 77.13,74.28 and 75.28 kJ/mol.Furthermore,the addition of catalysts reduces the hydrogen desorption activation energy(E_(a)^(de)).

Hydrogen storage thermodynamics and kinetics of as-cast Ce-Mg-Ni-based alloy

The reaction kinetics of alloys based on magnesium are known to be greatly improved by the partial substitution of Mg with rare earths and transition metals,particularly Ni.The enhanced superficial hydrogen dissociation rate,the weakened Mg-H bond and the lower activation energy following element replacement are thought to be related to the better performance.The experimental alloys Ce5Mg_(95-x)Ni_(x)(x=5,10,15)were smelted by the vacuum induction melting.The phase transformation and structural evolution of experimental alloys before and after reaction with hydrogen were char-acterized by X-ray diffraction,scanning electron microscopy and transmission electron microscopy.The cast specimens contain CeMg_(12),Mg and Mg_(2)Ni phases,and the increase in Ni content results in an obvious growth of Mg_(2)Ni phase.The isothermal and non-isothermal hydrogenation and dehydrogenation kinetics of the experimental specimens were investi-gated using the Sievert apparatus,differential scanning calorimetry and thermal gravimetric analyzer.The activation energy may be calculated using the Arrhenius and Kissinger equations.The experimental alloys have been shown to have good activation properties,with a reversible hydriding and dehydriding capacities of around 5.0 wt.%in the first cycle.The initial dehydrogenation temperature of MgH_(2) decreases from 557.5 to 537.7 K with changing Ni content from 5 to 15 at.%.The dehydrogenation activation energy also reduces from 77.09 to 62.96 kJ/mol,which explains the improved hydrogen storage performance caused by Ni substitution.It can be shown that the impact of Ni on the decomposition enthalpy of MgH_(2) is quite modest,with the absolute enthalpy(ΔHr)only decreasing from 78.48 to 76.15 kJ/mol.

Kinetics of Hydrogen Absorption in MmNi_（3．55）Co_（0．75）Mn_（0．4）Al_（0．3） Alloy

The kinetic process of MmNi3. 55Co0. 75Mn0. 4Al0. 3 alloy absorbing hydrogen in αand α+βphases at the temperature range of 22￣ 60℃ has been studied. The results show that the kinetic process is controlled by chemical reaction in the α phase and the mechanism of hydrogenation kinetics is not affected by initial hydrogen pressure. In the α+β phase region,the speed of hydrogen absorption is controlled by hydrogen diffusion in the hydride.A reaction rate equation and apparent activation energy have been obtained.

A Comparison Study of Hydrogen Storage Thermodynamics and Kinetics of YMg11Ni Alloy Prepared by Melt Spinning and Ball Milling

Melt spinning （MS） and ball milling （BM） were employed to fabricate YMg11Ni alloy, and their structures and hydrogen storage performances were examined. The results reveal that the as-spun and as-milled alloys both exhibit the nanocrystalline and amorphous structure. The as-milled alloy shows a larger hydrogen absorption capacity as compared with the as-spun alloy. More than that, the as-milled alloy exhibits lower onset hydrogen desorption temperature than the as-spun one, which are 549.8 and 560.9 K, respectively. Additionally, the as-milled alloy shows a superior hydrogen desorption property to the as-spun one. On the basis of the time needed by desorbing hydrogen of 3 wt% H2, for the as- milled alloy, it needs 1106, 456, 343, and 180 s corresponding to hydrogen desorption temperatures of 593, 613, 633, and 653 K. However, for the as-spun alloy, the time needed is greater than 2928, 842, 356, and 197 s corresponding to the same temperatures. Hydrogen desorption activation energies of as-milled and as-spun alloys are 98.01 and 105.49 kJ/mol, respectively, which is responsible for that the as-milled alloy possesses a much faster dehydriding rate. By means of the measurement of pressure-composition-temperature （P-C-T） curves, the dehydrogenation enthalpy change of the alloys prepared by MS （△Hoe（MS）） and BM （△Hdc（BM）） is 81.84 and 79.46 kJ/mol, respectively, viz. △Hde（MS） 〉 △Hoc（BM）.

Effect of milling duration on hydrogen storage thermodynamics and kinetics of ball-milled Ce-Mg-Ni-based alloy powders

To improve the hydrogen storage performance of CeMg12-type alloys, partially substituting Mg with Ni in the alloy was conducted. The way to synthesize the target alloy powders was the mechanical milling method, by which the CeMg11-Ni ＋ x wt% Ni （x = 100, 200） alloy powders with nanocrystalline and amorphous structure were obtained. The influence of the milling time and Ni content on the hydrogen storage properties of the alloys was discussed. The X-ray diffractometer and high-resolution transmission electron microscope were used to investigate the microstructures of the ball-milled alloys. The hydrogenation/dehydrogenation dynamics were studied using a Sievert instrument and a differential scanning calorimeter which was linked with a H2 detector. The hydrogen desorption activation energies of the alloy hydrides were evaluated by Arrhenius and Kissinger equations. From the results point of views, there is a little decline in the thermo- dynamic parameters （enthalpy and entropy changes） with the increase in Ni content. However, the alloys desorption and absorption dynamics are improved distinctly. What is more, the variation of milling time results in a dramatic influence on the hydrogen storage performances of alloys. Various maximum values of the hydrogen capacities correspond to different milling time, which are 5.805 and 6.016 wt% for the CeMgllNi ＋ x wt% Ni （x = 100, 200） alloys, respectively. The kinetics tests suggest that the hydrogen absorption rates increase firstly and then decrease with prolonging the milling time. The improvement of the gaseous hydrogen storage kinetics results from the decrease in the activation energy caused by the increase in Ni content and milling time.

A comparison study of hydrogen storage properties of as-milled Sm_5Mg_(41) alloy catalyzed by CoS_2 and MoS_2 nano-particles

The influences of the catalysts of CoS2 and MoB2 nano-particles on microstructure and hydrogen stor-age behaviors of as-milled SmsMg41 alloy have been compared in this work. The SmsMg41 ＋ 5 wt.% M （M = COS2, MoS2） alloys were prepared by milling the mechanical ground as-cast SmsMg41 alloy powders （particle size ≤75 μm） with 5 wt.% CoS2 or MoS2 nano-particles （particle size ≤ 30 nm）, respectively. The results demonstrate that the CoS2 and MoS2 nanoparticles are embedded into the alloy surface, which is nanostructure containing some crystal defects, such as dislocation, grain boundary and twin etc. Those microstructures play a beneficial role in reducing the total potential barrier that the hydrogen absorption or desorption reactions must overcome, hence improving the hydrogen storage kinetics of the alloys. The as-milled alloys are composed of SmsMg41 and SmMg3 phases, and ball milling refines their crys-tal grains. The MgH2 and Sm3H7 phases appear after hydrogenation, while Mg and Sm3H7 phases exist after dehydrogenation. The dehydriding activation energy of M = CoS2 and MoS2 alloys are 101.67 and 68.25 kJ/mol H2 respectively. The initial hydrogen desorption of M = CoS2 and MoS2 alloys are 252.9 ℃ and 247.8 ℃.The hydrogenation and dehydrogenation enthalpy changes of M = MoS2 alloy are a little smaller than that of MzCoS2 alloy. Therefore, the catalyst MoS2 can improve the as-milled SmsMg41 alloy in hydrogen storage property more effectively than C0S2.

A comparison study of hydrogen storage performances of SmMg_(11)Ni alloys prepared by melt spinning and ball milling

The melt spinning（MS） and ball milling（BM） technologies are thought to be efficient to prepare nanostructured Mg and Mg-based alloys for improving their hydrogen storage performances. In this paper, two technologies, viz. melt spinning and ball milling, were employed to fabricate the SmMg_（11）Ni alloy. The structure and hydrogen storage performance of these two kinds of alloys were researched in detail. The results reveal that the as-spun and milled alloys both contain nanocrystalline and amorphous structures. By means of the measurement of PCT curves, the thermodynamic parameters of the alloys prepared by MS and BM are ΔN_（Ms）（des） = 82.51 kJ/mol and ΔH_（BM）（des） = 81.68 kJ/mol, respectively, viz.ΔH_（MS）（des） 〉 ΔH_（BM）（des）. The as-milled alloy shows a larger hydrogen absorption capacity as compared with the as-spun one. The as-milled alloy exhibits lower onset hydrogen desorption temperature than the as-spun one. As to the as-milled and spun alloys, the onset hydrogen desorption temperatures are557.6 and 565.3 K, respectively. Additionally, the as-milled alloy shows a superior hydrogen desorption property than the as-spun one. On the basis of time that required by desorbing hydrogen of 3 wt% H_2, the as-milled alloy needs 1488.574,390 and 192 s corresponding to hydrogen desorption temperatures 593,613,633 and 653 K, while the as-spun alloy needs 3600,1020,778 and 306 s corresponding to the same temperatures. The dehydrogenation activation energies of the as-milled and spun alloys are 100.31 and105.56 kJ/mol, respectively, the difference of which is responsible for the much faster dehydriding rate of the as-milled alloy.

Structure and electrochemical properties of LaMgNi4-xCox(x=0-0.8)hydrogen storage electrode alloys

LaMgNi（4-x）Cox（x = 0-0.8） electrode alloys used for MH/Ni batteries were prepared by induction melting. The structures and electrochemical hydrogen storage properties of the alloys were investigated in detail.X-ray diffraction（XRD） and scanning electron microscopy（SEM） analysis show that LaMgNi4 phase and LaNi5 phase are obtained. The lattice parameters of the two phases increase first and then decrease with Co content increasing.The electrochemical properties of the alloy electrodes were measured by means of simulated battery tests. Results show that the addition of Co does not change the discharge voltage plateau of the alloy electrodes. However, the maximum discharge capacity increases from 319.9 mAh·g^-1（x = 0）to 347.5 mAh·g^-1（x = 0.4） and then decreases to331.7 mAh·g^-1（x = 0.8）. The effects of Co content on electrochemical kinetics of the alloy electrodes were also performed. The high rate dischargeability（HRD） first increases and then decreases with Co content increasing and reaches the maximum value（95.0 %） when x = 0.4. Test results of the electrochemical impedance spectra（EIS）,potentiodynamic polarization curves and constant potential step measurements of the alloy electrodes all demonstrate that when Co content is 0.4 at%, the alloy exhibits the best comprehensive electrochemical properties.

Hydrogen Storage Thermodynamics and Dynamics of Nd–Mg–NiBased Nd Mg_(12^-)Type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous Nd Mg_（12^-）type Nd Mg_（11）Ni＋ x wt% Ni（x=100, 200） hydrogen storage alloys were synthesized by mechanical milling. The effects of Ni content and milling time on hydrogen storage thermodynamics and dynamics of the alloys were systematically investigated. The gaseous hydrogen absorption and desorption properties were investigated by Sieverts apparatus and differential scanning calorimeter connected with a H_2 detector. Results show that increasing Ni content significantly improves hydrogen absorption and desorption kinetics of the alloys. Furthermore,varying milling time has an obvious effect on the hydrogen storage properties of the alloys. Hydrogen absorption saturation ratio（R^a_（10）; a ratio of the hydrogen absorption capacity in 10 min to the saturated hydrogen absorption capacity） of the alloys obtains the maximum value with varying milling time. Hydrogen desorption ratio（R^d_（20）, a ratio of the hydrogen desorption capacity in 20 min to the saturated hydrogen absorption capacity） of the alloys always increases with extending milling time. The improved hydrogen desorption kinetics of the alloys are considered to be ascribed to the decreased hydrogen desorption activation energy caused by increasing Ni content and milling time.

Effect of LaFeO_3 on hydrogenation/dehydrogenation properties of MgH_2

LaFeO3 was used to improve the hydrogen storage properties of Mg H2. The Mg H2＋20 wt.%La Fe O3 composite was prepared by ball milling method. The composite could absorb 3.417 wt.% of hydrogen within 21 min at 423 K while Mg H2 only uptaked 0.977 wt.% hydrogen under the same conditions. The composite also released 3.894 wt.% of hydrogen at 623 K, which was almost twice more than Mg H2. The TPD measurement showed that the onset dissociation temperature of the composite was 570 K, 80 K lower than the Mg H2. Based on the Kissinger plot analysis of the composite, the activation energy E des was estimated to be 86.69 k J/mol, which was 36 k J/mol lower than Mg H2. The XRD and SEM results demonstrated that highly dispersed La Fe O3 could be presented in Mg H2, benefiting the reduction of particle size and also acting as an inhibitor to keep the particles from clustering during the ball-milled process.

Study on electrochemical property of La_(0.75)Mg_(0.25)Ni_(2.85)Co_(0.45–x)(AlSn)_x (x=0.0,0.1,0.2,0.3) alloys

La_（0.75）Mg_（0.25）Ni_（2.85）Co_（0.45–x）（AlSn）_x（AlSn）_x（x=0.0,0.1,0.2,0.3） alloys were prepared by magnetic induction melting method, and the phase composition and electrochemical properties were investigated systematically. The alloys were mainly composed of LaNi5, La2Ni7 and LaNi3 phase, and the cell volume of LaNi5 increased with the Al and Sn contents. For the alloy corresponding to x=0.0, the Cmax and C150 were 348.9 and 185 mA h/g, respectively, then for the alloy electrode with x=0.2, even though the Cmax was only 309.0 mA h/g less than 348.9 mA h/g, the C150 of 231 mA h/g was much higher than 185 mA h/g. And the values of the limit current density, anodic peak current density and hydrogen diffusion coefficient of the La0.75Mg0.25Ni2.85Co0.35（AlS n）0.1（x=0.1） alloy were 1079.5, 1023.8 mA /g and 5.71×10–10 cm2/s, respectively. Which were the highest than that of any other electrodes. These results suggested that the kinetic property of the La_（0.75）Mg_（0.25）Ni_（2.85）Co_（0.45–x）（AlSn）_x（AlSn）_x（x=0.0, 0.1, 0.2, 0.3） electrodes could be improved effectively by adding moderate contents of Al and Sn.