Kinetics of Liquid-Phase Hydrogenation of Toluene Catalyzed by Hydrogen Storage Alloy MlNi_5

The kinetics of liquid-phase hydrogenation of toluene catalyzed by MlNi_5 was studied by investigating the influences of the reaction temperature and pressure on the mass transfer-reaction processes inside the slurry. The results show that the reaction rate accelerates when the reaction temperature increases, and reaches its maximum at about 490 K, but if temperature is higher than 510 K, the reaction rate decreases rapidly. The whole reaction process is controlled by the reaction at the surface of the catalyst particles. The mass transfer resistance at gas-liquid interface and that from the bulk liquid phase to the surface of the catalyst particle can be neglected. The apparent reaction rate is zero order for toluene concentration and first order for hydrogen concentration in the liquid phase. The kinetic model is obtained. The kinetic model fits the experimental data very well. The apparent activation energy of the hydrogen absorption reaction of MlNi_5-toluene slurry system is 41.01 kJ·mol^(-1).

Kinetics of Hydrogen Absorption in Hydrogen Storage Alloy

Hydrogenation kinetics of MLNi3.8(Co,Mn,Al)1.2 and MLNi3.7(Co,Mn,Al)1.2Cu0.1 alloy in α + β phase at the temperatUre range of 30 ～70 ℃ has been studied. The kinetic mechanism of hydrogen absorption is not affected by initial hydrogen pressure. Temperature does not influence the rate of hydrogen absorption obviously. In the prior and later period of hydrogen absorption the rate-controlling step is chemical reaction and hydrogen diffusion in the hydride phase respectively for MLNi3.8(Co,Mn,Al)1.2 alloy. Adding Cu, the rate-controlling step changes from chemical reaction to the nucleation and growth of β phase in the prior period and the process of hydrogen absorption still controlled by diffusion in the later period.

Shell and shrinking core kinetics model of Mg-based hydrogen storage alloys

The kinetics equation of the Mg-based hydrogen storage alloys (Mg-Ni-MO) was established by the shell and shrinking core model. The total coefficients of the kinetics equation of the hydrogen absorption and desorption process with shell diffusion as the controlling step were determined by semi-empirical and semi-theoretical methods, and the apparent activation energy of the hydrogen absorption process was obtained. The calculation results can well accord with the experimental data, and can well forecast the hydrogen storage capacity and absorption rate at different times. By using the kinetics equation, the effects of temperature and pressure on the hydrogen storage process can also be well understood. The kinetics equation is helpful for the design of the hydrogen storage container.

The electrochemical characteristics of AB_(4)-type rare earth-Mg-Ni-based superlattice structure hydrogen storage alloys for nickel metal hydride battery

Rare earth-Mg-Ni-based alloys with superlattice structures are new generation negative electrode materials for the nickel metal hydride batteries.Among them,the novel AB_(4)-type superlattice structure alloy is supposed to have superior cycling stability and rate capability.Yet its preparation is hindered by the crucial requirement of temperature and the special composition which is close to the other superlattice structure.Here,we prepare rare earth-Mg-Ni-based alloy and study the phase transformation of alloys to make clear the formation of AB_(4)-type phase.It is found Pr_(5)Co_(19)-type phase is converted from Ce_(5)Co_(19)-type phase and shows good stability at higher temperature compared to the Ce_(5)Co_(19)-type phase in the range of 930-970℃.Afterwards,with further 5℃increasing,AB_(4)-type superlattice structure forms at a temperature of 975℃by consuming Pr_(5)Co_(19)-type phase.In contrast with A_(5)B_(19)-type alloy,AB_(4)-type alloy has superior rate capability owing to the dominant advantages of charge transfer and hydrogen diffusion.Besides,AB_(4)-type alloy shows long lifespan whose capacity retention rates are 89.2%at the 100;cycle and 82.8%at the 200;cycle,respectively.AB_(4)-type alloy delivers 1.53 wt.%hydrogen storage capacity at room temperature and exhibits higher plateau pressure than Pr_(5)Co_(19)-type alloy.The work provides novel AB_(4)-type alloy with preferable electrochemical performance as negative electrode material to inspire the development of nickel metal hydride batteries.

Electrochemical performances of hydrogen storage alloys treated using a new milling technique

A new self-made additive of amidocyanogen-acetic salt was used in wet ball-grind technique （WBGT） for preparing hydrogen storage alloys, and the effect on the electrochemical performance of the alloy electrode was investigated in detail. It was found that the prepared electrode had perfect electrochemical performances, such as rapid activation, high capability, high-rate discharge （HRD） ability, and good stability. The first discharge capacitance at 0.2 C （throughout this study, n C rate means that the rated capacity of a hydrogen storage alloy （full capacity） is charged or discharged completely in 1/n h） reached 278 mAh·g^-1 and the discharge capacitance reached the maximum of 322 mAh·g^-1 only after two charge-discharge cycles. For the dry method, wet method, and WBGT, the high rate discharge （HRD） values （C5 c/C0.2c ratio） were approximately 0.59, 0.76, and 0.83, respectively. The stable discharge capacity at 3 C increased from 275 mAh·g^-1 （dry method）to 295 mAh·g^-1 （WBGT）.

Effect of commercial AB_5 alloy addition on the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys

A commercial AB5 hydrogen storage alloy was used as an additive to improve the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys. The effect of AB5 alloy addition on the phase structure, charge/discharge characteristics, and electrochemical kinetics of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy was investigated. The maximum discharge capacity of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 ＋ 4 wt.% AB5 electrode reaches 406 mAh/g. The anodic polarization, cyclic voltammetry, and potential step discharge experiments show that the electrochemical kinetics of the electrode with additives was promoted, with the LaNi5 phase of AB5 alloy acting as electro-catalytic sites in the electrode alloy. The high-rate dischargeability of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 ＋ 4 wt.% AB5 alloy electrode at 1100 mA/g reaches 60.9%, which is 9.4% higher than that of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy electrode. The cycling stability of the electrode with 4 wt.% AB5 alloy has also been improved

Influence of annealing temperature on electrochemical properties of rapidly quenched LPC(NiAlMn)_(4.25)Co_(0.75) hydrogen storage alloy electrodes

The influence of annealing temperature on the electrochemical properties and structure of the rapidly quenched LPC（NiAlMn）4.25Co0.75 hydrogen storage alloys was investigated, in which LPC represents the abbreviation of Nd-free La-Ce-Pr mischmetal after the extraction of most of Ce and Nd. After the annealing treatment between 700900 ℃ for rapidly quenched alloys, their discharge capacity becomes larger and the P-C-T plateau tends to be flatter and lower. The alloy annealed at 700 ℃ has the highest discharge capacity and flattest plateau. The analyses by X-ray diffraction （XRD）, different thermal analysis（DTA）, scanning electron microscopy （SEM） and transmission electron microscopy （TEM） indicate that the microstructure reversion and recrystallization occur during the heating, and their feature temperatures are 477 ℃ and 696 ℃ respectively. The annealing treatments make cell volume increase, dislocations and strain decrease, and the distribution of alloy composition become homogeneous.

Electrode properties and phase composition of Ti_(0.5)Ni_(0.25)Al_(0.25) hydrogen storage alloys and theoretical simulation

Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various temperatures.Electrochemical reaction kinetic parameters were also studied with proper electrochemical techniques.The influence of the secondary corrosion reaction on the anodic linear polarization measurement was also analyzed by theoretical simulation.The results show that,proper ball-milling with nickel powders is beneficial to electrochemical performance.The theoretical simulation proves that,the existence of the side reaction can disturb the measurement of electrochemical reaction kinetic parameters.

Tuning microstructures of Mg-Ce-Ni hydrogen storage alloys via Cu and carbon nanotube additions

Mg-based alloys are regarded as highly promising materials for hydrogen storage.Despite significant improvements of the properties for Mg-based alloys,challenges such as slow hydrogen absorption/desorption kinetics and high thermodynamic stability continue to limit their practical application.In this study,to assess hydrogen storage alloys with enhanced properties,incorporating both internal microstructure modulation through the preparation of amorphous/nanocrystalline structures and surface property enhancement with the addition of Cu and carbon nanotubes(CNTs),the kinetic properties of activation and hydrogenation,thermodynamic properties,and dehydrogenation kinetics are tested.The results reveal a complementary interaction between the added Cu and CNTs,contributing to the superior hydrogen storage performance observed in sample 7A-2Cu-1CNTs with an amorphous/nanocrystalline structure compared to the other experimental samples.Additionally,the samples are fully activated after the initial hydrogen absorption and desorption cycle,demonstrating outstanding hydrogenation kinetics under both high and low temperature experimental conditions.Particularly noteworthy is that the hydrogen absorption exceeds 1.8 wt.%within one hour at 333 K.Furthermore,the activation energy for dehydrogenation is decreased to 64.71 kJ·mol^(–1).This research may offer novel insights for the design of new-type Mg-based hydrogen storage alloys,which possess milder conditions for hydrogen absorption and desorption.

Phase transformation,thermodynamics and kinetics property of Mg90Ce5RE5(RE=La,Ce,Nd)hydrogen storage alloys

The Mg90Ce5 RE5(RE=La,Ce,Nd)alloys were prepared by a vacuum induction furnace and their micro structure,phase transformation,thermodynamics and kinetics property were systematically studied by XRD,SEM,TEM,and PCT characterization methods.The result shows that the activated alloys are composed of Mg/MgH2 and corresponding REH2+x with nanoscale.The REH2+x grain with Ce and La or Nd functional group have lower nucleation potential barriers than CeH2+x grains as the nucleation location,thus improve the hydrogen absorption kinetics of these alloys among which the Mg90Ce5Nd5 alloy can absorb 90%of the hydrogen within 2 min at 320℃.In addition,the Mg90Ce10 alloy has the lowest activation energy with 103.2 kJ mol-1 and the fastest desorption kinetics,which can release 5 wt%of the hydrogen within 20 min at 320℃.This is a correlation with grain size and the in-suit formed CeH2.73/CeO2 interface.Moreover,the co-doping Ce and La or Nd can effectively disorganize the thermodynamic stability of Mg-based hydrogen storage alloys to a certain degree,but the dehydrogenation kinetics of that still is restricted by the recombination energy of hydrogen ions on the surface.

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.

A novel method towards improving the hydrogen storage properties of hypoeutectic Mg-Ni alloy via ultrasonic treatment

Ultrasonic treatment has great contributions on modifying the morphology,dimension and distribution of constituent phases during solidification,which serve as dominate factors influencing the hydrogen storage performance of Mg-based alloys.In this research,ultrasonic treatment is utilized as a novel method to enhance the de-/hydriding properties of Mg-2Ni(at.%)alloy.Due to ultrasonic treatment,the microstructure of as-cast alloy is significantly refined and homogenized.Ascribing to the increased eutectic boundaries and shortened distance insideα-Mg for hydrogen atoms diffusion,the hydrogen uptake capacities and isothermal de-/hydriding rates improve effectively,especially at lower temperature.The peak desorption temperature reduces from 392.99°C to 345.56°C,and the dehydriding activation energy decreases from 101.93 k J mol^(-1)to 88.65 k J mol^(-1).Weakened hysteresis of plateau pressures and slightly optimized thermodynamics are determined from the pressure-composition isotherms.Owing to the refined primary Mg,a larger amount of hydrogen with the higher hydriding proportion is absorbed in the first stage when hydrides nucleate in eutectic region and grow on primary Mg periphery subsequently before MgH2colonies impinging,resulting in the enhancement of hydrogenation rates and capacities.

Influences of substituting Ni with M(M=Cu,Co,Mn)on gaseous and electrochemical hydrogen storage kinetics of Mg_(20)Ni_(10) alloys

In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4)alloys prepared by melt spinning has been carried out.The analysis of XRD and TEM reveals that 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 nanocrystalline and amorphous structure when M content x=4,indicating that the substitution of M(M=Co,Mn)for Ni facilitates the glass formation in the Mg2Ni-type alloy.Besides,all the as-spun alloys have a major phase of Mg2Ni but M(M=Co,Mn)substitution brings on the formation of some secondary phases,MgCo2 and Mg phases for M=Co as well as MnNi and Mg phases for M=Mn.Based upon the measurements of the automatic Sieverts apparatus and the automatic galvanostatic system,the impacts engendered by M(M=Cu,Co,Mn)substitution on the gaseous and electrochemical hydrogen storage kinetics of the alloys appear to be evident.The gaseous hydriding kinetics of the alloys first rises and then declines with the growing of M(M=Cu,Co,Mn)content.Particularly,the M(M= Mn)substitution results in a sharp drop in the hydriding kinetics when x=4.The M(M=Cu,Co,Mn)substitution ameliorates the dehydriding kinetics dramatically in the order(M=Co)>(M=Mn)>(M=Cu).The electrochemical kinetics of the alloys visibly grows with M content rising for(M=Cu,Co),while it first increases and then declines for(M=Mn).

Influences of molybdenum substitution for cobalt on the phase structure and electrochemical kinetic properties of AB_5-type hydrogen storage alloys

The effects of the partial replacement of Co with Mo on the phase structure and electrochemical kinetic properties of La0.35Ce0.65Ni3.54Co0.80-xMn0.35Al0.32Mox （x=0.00, 0.10, 0.15, 0.20, 0.25） hydrogen storage alloys prepared by arc-melting method were sys-tematically studied in this paper. The X-ray diffraction （XRD） showed that after partial substitution of Mo for Co, the alloys remained a single LaNi5 phase with a hexagonal CaCu5-type structure. The P-C isotherms indicated that the equilibrium pressure gradually decreased with in-creasing of Mo content. Electrochemical studies showed that the substitution of Mo for Co could greatly increase discharge capacity, improve activation ability and reduce self-discharge of alloy electrodes. The alloy with x=0.25 exhibited a higher rate dischargeability （HRD1200= 50.9%）. Moreover, Mo is a vital element in favor of kinetic properties of AB5-type hydrogen storage alloys. As Mo content increased, the ex-change current density I0, the hydrogen diffusion rate gradually increased.

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.

Enhancing (de)hydrogenation kinetics properties of the Mg/MgH_(2) system by adding ANi_(5)(A=Ce,Nd,Pr,Sm,and Y) alloys via ball milling

Magnesium(Mg)-based alloys have already been widely studied as the hydrogen storage materials because of their high reversible hydrogen storage capacity,low cost,light weight,etc.However,the poor de/hydrogenation kinetic properties dramatically hinder the practical applications.In this work,the MgH_(2)-ANi_(5)(A=Ce,Nd,Pr,Sm,and Y) composites were prepared by a high-energy ball milling method.which can effectively refine the particle size thus improving the kinetic properties.Experimental results reveal that the MgH_(2)-ANi_(5) composites mainly consist of Mg_(2)NiH_(4),MgH_(2) and rare earth(RE) hydride,which will be dehydrogenated to form Mg_(2)Ni,Mg and stable RE hydride reversibly.Accordingly,the asmilled MgH_(2)-ANi_(5)(A=Ce,Nd,Pr,Sm,and Y) composites with various A-elements can respectively contribute to a reversible hydrogen storage capacity of 6.16 wt%,5.7 wt%,6.21 wt%,6.38 wt%,and 6.5 wt%at a temperature of 300℃,and show much better kinetic properties in comparison to the pure MgH_(2) without any additive.In-situ formed Mg_(2) Ni and stable RE hydride(such as CeH_(2.73) and YH_(2)) might act as effective catalysts to significantly improve the hydrogen storage properties of MgH_(2).The present work provides a guideline on improving the kinetic properties of the Mg-based hydrogen storage alloys.

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.

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)).

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.

Kinetics in Mg-based hydrogen storage materials:Enhancement and mechanism

Mg-based materials have been intensively studied for hydrogen storage applications due to their high energy density up to 2600 Wh/kg or 3700 Wh/L.However,the Mg-based materials with poor kinetics and the necessity for a high temperature to achieve 0.1 MPa hydrogen equilibrium pressure limit the applications in the onboard storage in Fuel cell vehicles(FCVs).Over the past decades,many methods have been applied to improve the hydriding/dehydriding(H/D)kinetics of Mg/MgH 2 by forming amorphous or nanosized particles,adding catalysts and employing external energy field,etc.However,which method is more effective and the intrinsic mechanism they work are widely differing versions.The hydrogenation and dehydrogenation behaviors of Mg-based alloys analyzing by kinetic models is an efficient way to reveal the H/D kinetic mechanism.However,some recently proposed models with physical meaning and simple analysis method are not known intimately by researchers.Therefore,this review focuses on the enhancement method of kinetics in Mg-based hydrogen storage materials and introduces the new kinetic models.