Comparative study on the hydrogen storage performance of as-milled MgRENi rapid quenched alloy catalyzed by metal sulfides

The composites of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)as-quenched alloy and 3 wt.%M(M=CoS,CoS_(2),MoS_(2))catalyst were prepared by high-speed vibration ball mill.The effects of metal sulfides on the hydrogenation and dehydrogenation dynamics of alloys were compared.The results show that the as-milled composites contain a large number of amorphous embedded by a small amount of nanocrystals,and there are many point defects.After ball milling,the crystal grain size in the composites containing CoS is relatively larger,followed by CoS_(2)and MoS_(2)again.After hydrogenation,the amorphous phase is crystallized to form Mg_(2)NiH_(4),YH_(3),Pr_(8)H_(18.96),Sm_(3)H_7,Mg,Co or Mo phases,however,Mg_(2)Ni,YH_(2),PrH_(2)and Ni_(3)Y phases appeared after dehydrogenation.The maximum hydrogenation capacity of the composites containing CoS,CoS_(2)and MoS_(2)are 3.939,4.265 and 4.507 wt.%,respectively.The hydrogenation saturation ratio of composite containing MoS_(2)is higher than that of the composites containing CoS and CoS_(2).The dehydrogenation activation energy of the composites containing CoS,CoS_(2)and MoS_(2)is 107.76,68.43 and 63.28 kJ.mol^(-1).H_(2).On the improvement of hydrogen storage performance of Mg_(20)Pr_(1)Sm_(3)Y_(1)Ni_(10)alloy,the catalytic effect of MoS_(2)sulfide is better than that of CoS_(2)sulfide,and which is better than CoS sulfide.

Effect of ball milling on hydrogen storage of Mg_3La alloy

Hydrogen storage and microstructure of ball milled Mg3La alloy were investigated by X-ray diffraction and pressure-composition-isotherm measurement. The ball milled Mg3La alloy could absorb hydrogen up to 4wt.% at 300 ℃ for the first time, along with a decomposing course. Following tests showed that the average reversible hydrogen storage capacity was 2.7wt.%. The enthalpy and entropy of dehydrogenation reaction of the decomposed ball milled Mg3La and hydrogen were calculated. XRD patterns indicated the existence of MgH2 and LaH3 in the decomposed hydride and the formation of Mg when hydrogen was desorbed. After the first hydrogenation, all the latter hydrogenation/dehydrogenation reactions could be taken place between Mg and MgH2. The ball milled Mg3La alloy exhibited better hydriding kinetics than that of the as-cast Mg3La alloy at room temperature. The kinetic curve could be well fitted by Avrami-Erofeev equation.

Hydrogen storage behavior of nanocrystalline and amorphous La-Mg-Ni-based LaMg_(12)-type alloys synthesized by mechanical milling

Nanocrystalline and amorphous LaMg11Ni+x%Ni(x=100,200,mass fraction)alloys were synthesized by mechanicalmilling.The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system.The gaseous hydrogen absorption and desorption properties were investigated by Sievert’s apparatus and differential scanningcalorimeter(DSC)connected with a H2detector.The results indicated that increasing Ni content significantly improves the gaseousand electrochemical hydrogen storage performances of the as-milled alloys.The gaseous hydrogen absorption capacities andabsorption rates of the as-milled alloys have the maximum values with the variation of the milling time.But the hydrogen desorptionkinetics of the alloys always increases with the extending of milling time.In addition,the electrochemical discharge capacity andhigh rate discharge(HRD)ability of the as-milled alloys both increase first and then decrease with milling time prolonging.

Gaseous hydrogen storage thermodynamics and kinetics of RE-Mg-Ni-based alloys prepared by mechanical milling

Nanocrystalline/amorphous La Mg11Ni+x Ni(x=100%, 200%, mass fraction) composite hydrogen storage alloys were synthesized by ball milling technology. The effects of Ni content and milling time on the gaseous hydrogen storage thermodynamics and dynamics of the alloys were systematically investigated. The hydrogen desorption properties were studied by Sievert's apparatus and a differential scanning calorimeter(DSC) connected with a H2 detector. The thermodynamic parameters(ΔH and ΔS) for the hydrogen absorption and desorption of the alloys were calculated by Van't Hoff equation. The hydrogen desorption activation energy of the alloy hydride was estimated using Arrhenius and Kissinger methods. The results indicate that a variation in the Ni content has a slight effect on the thermodynamic properties of the alloys, but it significantly improves their absorption and desorption kinetics performances. Furthermore, varying milling time clearly affects the hydrogen storage properties of the alloys. All the as-milled alloys show so fast hydrogen absorption rate that the absorbed amount in 10 min reaches to at least more than 95% of the saturated hydrogen absorption capacity. Moreover, the improvement of the gaseous hydrogen storage kinetics of the alloys is found to be ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and prolong milling time.

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.

Hydrogen storage properties of nanocomposite Mg-Ni-MnO_2 made by mechanical milling

The hydrogen storage properties of the nanocomposite Mg 95 Ni 3(MnO 2) 2 (mass fraction, %) were studied. The temperature changes in hydriding/dehydriding process were investigated. The nanocomposite was fabricated by ball milling process of mixed elemental Mg, Ni and oxide maganese MnO 2 under hydrogen pressure (approximately 0.6?MPa). The hydrogen absorption and desorption properties of the samples milled for various times were investigated. A remarkable enhancement of hydrogen absorption kinetics and low operational desorption temperature have been found after the sample milled for over 57?h. For example, this nanocomposite can absorb hydrogen more than 6.0% (mass fraction) in 60?s at 200?℃ under 2.0?MPa, and desorption capacity also exceeds 6.0% (mass fraction) in 400?s at 310?℃ under 0.1?MPa. The storage properties of samples milled for various times were studied and the kinetics of the samples were analyzed.

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）.

Hydrogen storage performances of as-milled REMg_(11)Ni(RE=Y, Sm) alloys catalyzed by MoS_2

To compare the hydrogen storage performances of as-milled REMg11Ni-5MoS2(mass fraction)(RE=Y,Sm)alloys,which were catalyzed by MoS2,the corresponding alloys were prepared.The hydrogen storage performaces of these alloys were measured by various methods,such as XRD,TEM,automatic Sievert apparatus,TG and DSC.The results reveal that both of the as-milled alloys exhibit a nanocrystalline and amorphous structure.The RE=Y alloy shows a larger hydrogen absorption capacity,faster hydriding rate,lower initial hydrogen desorption temperature,superior hydrogen desorption property,and lower hydrogen desorption activation energy,which is thought to be the reason of its better hydrogen storage kinetics,as compared with RE=Sm alloy.

Hydrogen storage properties of ball-milled Mg-based composite with PdCl_2 additive

Mg-25 wt% Mg2Ni composite was prepared by sintered method, hydrided at 613 K and then ball-milled with 1.5 wt% PdC12 additive for 51 h. The effects of PdCl2 on the hydriding and dehydriding behavior of Mg-25 wt% Mg2Ni composite were investigated. The absorption and desorption rate of the composite with PdCl2 is fast and the hydrogen storage capacity is more than that of the composite without PdCl2. The maximum hydrogen storage capacity reached 3.48 wt% at 373 K, and 5.05 wt% H at 453 K, respectively. The improvement of sorption and desorption kinetics is attributed to the catalytic effect of PdCl2, and the grain refining and lattice strain introduced by ball milling.

Storage and Remobilization of Nitrogen by Chinese Jujube(Z. jujuba Mill. var. inermis Rehd) Seedling as Affected by Timing of ^(15)N Supply

Winter jujube orchard nitrogen （N） management aims at increasing N reserves to meet the tree＇s growth requirements. Fertilization strategies should maximize the efficiency of fertilizers, including the choice of the optimal timing of N supply. ^15N-urea was applied to winter jujubes on Jinsixiaozao jujubes rootstock to evaluate the effect of application timing on Nstorage and remobilization in mature trees in pot culture. The treatments consisted of ground application before budding （BB）, during fruit core-hardening stage （FCH）, and fruit rapid-swelling stage （FRS）. Nitrogen-use efficiency of treatments were significantly different, which were 2.42% （BB）, 9.77% （FCH）, and 9.01% （FRS） in the dormant and 5.20% （BB）, 16.16% （FCH）, and 10.30% （FRS） in the following full-bloom. N supply in the pre-harvest helped to increase N-reserves of trees and then translocate to the new growth organs the following year. The largest amount of ^15N was detected in the roots and trunks. In all the treatments, the partition rates were highest in coarse roots, which were 30.43% （BB）, 38.61% （FCH）, and 40.62% （FRS）, respectively. ^15N stored in roots and trunks was used by jujube trees to sustain new growth in the following full-bloom. ^15N applied before budding resulted in lower Ndff% in perennial organs （trunks and coarse roots） sampled in the following full-bloom, but fine roots had highest Ndff% （1.28%）. Other organs recovered similar amount of Ndff%. In contrast, FCH and FRS treatments led to higher Ndff% （4.01-5.15%） in the new growth organs （new growth branches, deciduous spurs, leaves and flowers）, but lower Ndff% in perennial branches （1.49-2.89%）. With the delay of ^15N-urea application time, ^15N increased the partitioning to roots. FCH treatment increased N-storage in perennial organ during winter, which should be remobilized to sustain new growth the following spring.

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 properties of MgH2 co-catalyzed by LaH3 and NbH

To improve the hydrogen storage properties of Mg-based alloys, a composite material of MgH_2 + 10wt%LaH_3 + 10wt%NbH was prepared by a mechanical milling method. The composite exhibited favorable hydrogen desorption properties, releasing 0.67wt% H2 within 20 min at 548 K, which was ascribed to the co-catalytic effect of LaH_3 and NbH upon dehydriding of MgH_2. By contrast, pure MgH_2, an MgH_2 + 20wt%LaH_3 composite, and an MgH_2 + 20wt%NbH composite only released 0.1wt%, 0.28wt%, and 0.57wt% H2, respectively, under the same conditions. Analyses by X-ray diffraction and scanning electron microscopy showed that the composite particle size was small. Energy-dispersive X-ray spectroscopic mapping demonstrated that La and Nb were distributed homogeneously in the matrix. Differential thermal analysis revealed that the dehydriding peak temperature of the MgH_2 + 10wt%LaH_3 + 10wt%NbH composite was 595.03 K, which was 94.26 K lower than that of pure MgH_2. The introduction of LaH_3 and NbH was beneficial to the hydrogen storage performance of MgH_2.

Structural and Electrochemical Characteristics of Mg_(0.94)La_(0.06)Ni Alloy Prepared by Ball Milling

The amorphous Mg_(0.94)La_(0.06)Ni alloy was synthesized by ball milling for different time at 400 r·min^(-1). Electrochemical performances of the alloy electrodes were investigated and the results show that the specimens would reach their maximum electrochemical discharge capacities at the first charge/discharge cycle. The cyclic tests and X-ray diffraction (XRD) results show that discharge capacities would decrease rapidly due to the crystallization of the amorphous and the oxidization of magnesium on the particle surface during the electrochemical charge/discharge cycling. In addition, the DTA and SEM results reveal that the thermal stabilities will be improved and the size of the alloy will be decreased with the ball-milling time. The amorphous Mg_(0.96)La_(0.04)Ni alloy prepared by ball milling for 40 h at 400 r·min^(-1) shows the best electrochemical properties.

Changes in Physicochemical,Cooking and Sensory Characteristics of Rice Shifted from Low-temperature Storage

The physicochemical, cooking, and sensory characteristics of stored rice were measured in order to investigate the quality changes in it after low-temperature storage. The quality of the stored rice was compared to that of the rice stored at ambient temperature(20℃, 30%–70% RH) at a 25 d interval during 200 d of storage. The rice was stored in a temperature controller at 4℃ for 3 months and later under a simulated condition similar to that of the main rice consumption areas in China(35℃, 80% RH and 30℃, 70% RH). The results showed that the fatty acid value, b value, and moisture content of rice stored at 35℃, 80% RH and 30℃, 70% RH had increased significantly, whereas its L value had decreased as compared to the rice stored at ambient temperature. Higher temperature storage caused a greater water uptake, whereas the dry mass in the residual cooking water notably reduced under the storage at 35℃ as compared to that at 20℃. Hardness increased and adhesiveness reduced under the storage at 35℃ as compared to that at 20℃. The shelf life of the stored rice which was shifted from a low temperature to three storage conditions used in this study was 75 d, 100 d and 150 d, respectively, in the main rice consumption areas of China.

Significantly improved hydrogen storage behaviors in MgH_(2) with Nb nanocatalyst

The study explores the excellent modification effect of Nb nanocatalyst prepared via surfactant assisted ball milling technique(SABM)on the hydrogen storage properties of MgH_(2).Optimal catalyst doping concentration was determined by comparing onset decomposition temperature,released hydrogen capacity,and reaction rate for different MgH_(2)-ywt%Nb(y=0,3,5,7,9)composites.The MgH_(2)-5wt%Nb composite started releasing hydrogen at 186.7℃ and a total of 7.0wt%hydrogen was released in the dehydrogenation process.In addition,5wt%Nb doped MgH_(2) also managed to release 4.2wt%H_(2) within 14 min at 250℃ and had the ability to absorb 4.0wt%hydrogen in 30 min at 100℃.Cycling tests revealed that MgH_(2)-5wt%Nb could retain 6.3wt%H_(2) storage capacity(89.2%)after 20 cycles.Dehydrogenation and hydrogenation activation energy values were decreased from 140.51±4.74 and 70.67±2.07 kJ·mol^(−1) to 90.04±2.83 and 53.46±3.33 kJ·mol^(−1) after doping MgH_(2) with Nb,respectively.Microstructure analysis proved that homogeneously distributed NbH acted as active catalytic unit for improving the hydrogen storage performance of MgH_(2).These results indicate SABM can be considered as an option to develop other nanocatalysts for energy related areas.

MgH_2-Ti/Cr(AMORPHOUS)COMPOSITE FOR HYDROGEN STORAGE

Ti/Cr (atomic ratio 3:4) amorphous alloy was prepared by ball milling the rapidly quenched Ti/Cr ribbons for 30h, and then milled with MgH_2 for 50 h under Ar atmosphere to obtain MgH_2-30wt. % Ti/Cr composite. The XRD results indicate that MgH_2 decomposed partly during ball milling process. The brittle MgH_2 and the mechanical driving force resulted in a highly dispersive distribution of the Ti/Cr amorphous phase in the Mg matrix. The favorable hydrogenation performance is mainly attributed to the com...

Sorption properties of Mg-Ni-CrCl_3 hydrogen storage composite

Hydrogen absorption composite powder of Mg incorporated with Ni and CrCl3 （88∶10∶2 in mass ratio） was prepared by reactive milling in hydrogen atmosphere. Hydriding/dehydriding performances were measured by self-made apparatus. The results show that reactive milling and multi-component addition of Ni and CrCl3 reduce the stability of hydride and improve the sorption performance of Mg-based materials. With powder milled for 60h, hydriding basically completes within 300s （250℃, 2.0MPa） and phase transformation fraction reaches 0.78. The phase transformation rate of hydriding/dehydriding progress increases significantly with the reduced particles size of powder while good kinetics of dehydriding at a relatively low temperature is gained with small grain size of hydride. Rapid temperature variations in a short span of time resulted from remarkable calorific effects of rapid phase transformation are detected in hydriding/dehydriding progress. The results of thermogravimetric and differential scanning calorimetric（TG/DSC） indicate that the onset temperature of desorption of composite milled for 100h is 272℃.

AB_5-type Hydrogen Storage Alloy Modified with Ti/Zr Used as Anodic Materials in Borohydride Fuel Cell

Fuel cell using borohydride as the fuel has received much attention. AB5-type hydrogen storage alloy used as the anodic material instead of noble metals has been investigated. In order to restrain the generation of hydrogen and enhance the utilization of borohydride, Ti/Zr metal powders has been added into the parent LmNi4.78Mn0.22 （where Lm is La-richened mischmetal） alloy （LNM） by ball milling and heat treatment methods. It is found that the addition of Ti/Zr metal powders lowers the electrochemical catalytic activity of the electrodes, at the same time, restrains the generation of hydrogen and enhances the utilization of the fuel. All the results show that the hydrogen generation rate or the utilization of the fuel is directly relative to the electrochemical catalytic activity or the discharge capability of the electrodes. The utilization of the fuel increases with discharge current density. It is very important to find a balance between the discharge capability and the utilization of the fuel.

Electrochemical Properties of CeMg_(12)+x%Ni Composites (x=0～200) Prepared by Ball-Milling

The electrochemical properties of the as-cast and ball-milled CeMg12+x%(mass fraction) Ni (vs. CeMg12) (x=0, 50, 100 and 200) composites were investigated. The microstructure and discharge capacity of the ball-milled CeMg12+x%Ni composites differ greatly depending on the amount of Ni introduced during ball-milling. The more nickel powder added, the more advantageous for the formation of the amorphous structure. And the discharge capacities of the ball-milled composites increase with increasing amount of nickel added. After 90 h ball-milling, the CeMg12+200% Ni composite exhibits a high discharge capacity of 1170 mAh·g-1(CeMg12)-1 at 303 K. The improvement of electrochemical capacity is attributed to the formation of a homogeneous amorphous structure as well as the modification of the surface state after Ni addition.

Effect of Ball Milling Time on Microstructure and Hydrogen Storage Properties of Nd_(5)Mg_(41)Ni Alloy

Mg-based alloys must be dehydrogenated at high pressure and temperatures, limiting their practical application. In this paper, Nd_(5)Mg_(41)Ni alloy was prepared by vacuum melting, and the as-cast alloy was ball milled for 5 h, 10 h, 15 h, and 20 h. The effect of ball milling time on the microstructure and hydrogen storage properties of the alloy was systematically studied. The alloy comprises Nd_(5)Mg_(41), NdMg_(12), NdMg_(3), and Mg_(2)Ni phases. The Nd_(5)Mg_(41)Ni alloy milling for 10 h can reach 95% of the saturated hydrogen absorption at 553 K by 40 s, and the alloy can desorb hydrogen only by 20 min. The dehydrogenation activation energy is only 99.9 kJ/mol H_(2). Ball milling makes the alloy produce many nanocrystalline and amorphous structures. The nano-grain boundary provides a channel for the diffusion of hydrogen atoms, and the high energy at the grain boundary provides energy for the phase deformation nucleus. Ball milling leads to the refinement of alloy particles and shortens the diffusion distance of hydrogen atoms to the interior of alloy particles. Defects such as twins and dislocations generated by milling provide energy for the phase deformation nucleus during the hydrogen absorption and desorption.