Hydriding and Dehydriding Characteristics of Mechanically Alloyed LaMg_(17) Ni Composite Material

Magnesiumandmagnesiumalloyshavebeenin vestigatedashydrogenstoragematerialsforseveralde cadesbecausefarmorehydrogenbyweightcanbestoredinthemthaninmostoftheothercurrentlyknownhydrogenstoragealloys .Moreover ,thehighnaturalabundanceofMg ,itslightmassandenviron mentalcompatibilitypotentiallymakemagnesiumoneofthemostprospectivecandidatesforfuturehydrogenstoragematerials .Unfortunately ,thepracticalappli cationofMganditsalloyshasbeenlimitedonlytocertainstoragedevicebecauseoftheirpoorhydriding dehydr…     

氢化燃烧合成与机械合金化复合制备LaMg_(11.5)Ni_(0.5)储氢材料

采用氢化燃烧合成和机械球磨复合制备了LaMg11.5Ni0.5三元储氢材料,物相分析可知,该体系由MgH2、Mg、Mg2NiH4,Mg2NiH0.3,LaH2以及少量LaNi5H0.3构成.氢化燃烧合成产物LaMg11.5Ni0.5经20h球磨后,在423K时,100s内达到饱和吸氢量3.42%(质量分数);在523K时,1 800s内放氢基本完全,放氢量为3.29%(质量分数).研究表明,该产物在523K时的放氢过程受界面移动过程控制.     

Phase evolution,hydrogen storage thermodynamics and kinetics of ternary Mg_(90)Ce_5Sm_5 alloy

Greatly stable thermodynamics and sluggish kinetics impede the practical application of Mg-based hydrogen storage alloys.The modifications of composition and structure are important strategies in turning these hydrogen storage properties.In this study,Mg-based Mg_(90)Ce_5 Sm_5 ternary alloy fabricated by vacuum induction melting was investigated to explore the performance and the reaction mechanism as hydrogen storage material by X-ray diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM) and pressure-composition isotherms(PCI) measurements.The results indicate that the Mg-based Mg_(90)Ce_5 Sm_5 ternary alloy consists of two solid solution phases,including the major phases(Ce,Sm)5 Mg_(41) and the minor phases(Ce,Sm)Mg_(12).After hydrogen absorption,these phases transform into the MgH2 and(Ce,Sm)H_(2.73) phase,while after hydrogen desorption,the MgH2 transforms into the Mg phase,but the(Ce,Sm)H2.73 phases are not changed.The alloy has a reversible hydrogen capacity of about 5.5 wt% H_2 and exhibits well isothermal hydrogen absorption kinetics.Activation energy of 106 kJ/mol was obtained from the hydrogen desorption data between 573 and 633 K,which also exhibits the enhanced kinetics compared with the pure MgH2 sample,as a result of bimetallic synergy catalysis function of(Ce,Sm)H_(2.73) phases.The rate of hydrogen desorption is controlled by the release and recombination of H_2 from the Mg surface.Furthermore,the changes of enthalpy and entropy of hydrogen absorption/desorption were calculated to be-80.0 kJ/mol H_2,-137.5 J/K/mol H_2 and 81.2 kJ/mol H_2,139.2 J/K/mol H_2,respectively.     

A study on hydrogen storage and electrochemical properties of La_（0.55）Pr_（0.05）Nd_（0.15）Mg_（0.25）Ni_（3.5） （Co_（0.5）Al_（0.5））_x （x=0.0, 0.1, 0.3, 0.5） alloys

The La0.55Pr0.05Nd0.15Mg0.25Ni3.5(Co0.5Al0.5)x(x=0.0, 0.1, 0.3, 0.5) alloys were prepared by magnetic levitation melting under an Ar atmosphere, and the effects of Co and Al on the hydrogen storage and electrochemical properties were systematically investigated by pressure composition isotherms, cyclic voltammetry, Tafel polarization and electrochemical impedance spectroscopy testing. The results showed that the alloy phases were mainly consisted of (La,Pr)(Ni,Co)5, LaMg2Ni9, (La,Nd)2Ni7 and LaNi3 phases, and the cell volumes of (La,Pr)(Ni,Co)5, LaMg2Ni9, (La,Nd)2Ni7 and LaNi3 phases expanded with Co and Al element added. The hydrogen storage capacity initially increased from 1.36 (x=0) to 1.47 wt.% (x=0.3) and then decreased to 1.22 wt.% (x=0.5). The discharge capacity retention and cycle stability of the alloy electrodes were improved with the increase of Co and Al contents. The La0.55Pr0.05Nd0.15Mg0.25Ni3.5(Co0.5Al0.5)0.3 alloy electrode possessed better electrochemical kinetic characteristic.     

Effect of ball milling on hydrogen storage of Mg3La 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.     

Hydriding/dehydriding properties of NdMgNi alloy with catalyst CeO2

Hydrogen storage composites Nd2Mg17-50 wt.%Ni-x wt.%CeO2（x=0, 0.5, 1.0, 1.5, 2.0） were obtained by induction-ball milling method. The catalytic effect of CeO₂ on hydriding kinetics of Nd₂Mg17-50 wt.%Ni composite was investigated. X-ray diffraction（XRD） and high resolution transmission electron microscopy（HRTEM）, selected area electron diffraction（SAED） analyses showed that Nd₂Mg17-50 wt.%Ni alloy had a multiphase structure, consisting of NdMg12, NdMg₂Ni, Mg₂Ni and Ni phases and the addition of catalyst CeO₂ prompted the composites to be partly transformed into amorphous strucutre. The CeO₂ improved the maximum hydrogen capacity of Nd₂Mg17-50 wt.%Ni alloy from 3.192 wt.% to 3.376 wt.%（x=1.0）. What’s more, the increment of diffusion coefficient D led to the faster hydriding kinetics, which was calculated by Avrami-Erofeev equation. The dehydrogenation temperature reduced from 515.54 to 504.72 K was mainly caused by the decrease of activation energy from 93.28 to 69.36 kJ /mol, which was proved by the Kissinger equation.     

Effect of Preparation Methods on Hydriding Properties of La1.5Mg17 Ni0.5 Composite Materials

La1.5Mg17Ni0.5 hydrogen storage materials were prepared by hydriding combustion synthesis (HCS) and mechanical alloying (MA) method respectively. The experimental results show that the hydrogen absorption properties of La1.5Mg17Nio.5 prepared by MA are better than that by HCS. La1.5Mg17Nio.5 prepared by MA can absorb 6.73 mass% hydrogen at 523 K within 1 min, and 4.92 mass% hydrogen at 423 K. The improvement of hydriding properties of La1.5Mg17Ni0.5alloy prepared by MA can be ascribed to the formation of nano-crystalline and defects during the mechanical alloying.     

Effect of Ni/（La＋Mg） Ratio on Structure and Electrochemical Performance of La-Mg-Ni Alloy System

As the alloy with the most suitable Ni/(La+ Mg) ratio has higher capacity and good cycle stability,theeffects of Ni/(La+Mg) ratios on the electrochemical performances of the La0.80 Mg0.20 Nix (x= 3.5 to 5.0) alloys have been investigated to find the most suitable Ni/(La+ Mg) ratio.The results of XRD and SEM observations show that the phase composition of the alloys varies with different Ni/(La+Mg) ratios.When Ni/(La+Mg) is notmore than 4.25,all the alloys contain LaNi5 and (La,Mg)2Ni7 phases,in addition,the LaMg and (La,Mg)Ni3 phases exist in the x=3.5 and 3.75 alloys,respectively.The LaMg2Ni9 phase exists in the x=4.25 alloy.There are the LaNi5 and LaMg2 Ni9 phases in the x= 4.5,4.75,and 5.0 alloys.The phase abundance and cell volume change with different Ni content.When the Ni/(La+Mg) ratio is not more than 4.25,the alloys possess excellent activation capability,however,the activation capabilities of the alloys decrease with a further increase in the Ni/(La+Mg)ratio.With increasing the Ni/(La+ Mg) ratio,the maximum discharge capacities,the medium voltages,and the cycle stabilities of the alloys first increase and then decrease.When the Ni/(La+Mg) ratio is 3.75,the corresponding alloyhas the maximum discharge capacity among all the alloys.However,the cycle stability of the Ni/(La+ Mg)= 4.0 alloy is better than that of the others.     

硼的添加对Mg2Ni储氢合金吸放氢性能的影响

镁系储氢合金有着价格低廉、储氢量大等优点,作为机载储氢材料有着广泛的应用前景,但其过高的氢分解温度,过慢的分解速度等缺点制约着实际应用.采用机械球磨制备出Mg2 Ni-xB(x =0％,1％,5％,10％,15％)系列储氢合金.通过XRD分析了合金的物相结构,采用P-C-T测试仪测定了合金的吸放氢性能,研究了添加不同含量的B对Mg2Ni合金吸放氢性能的影响.研究结果表明,B的添加对合金在200和300℃下吸放氢性能的改善作用不明显,但添加B的合金在400℃下的吸氢量均较Mg2Ni高,B的添加量由1％增至15％的合金吸氢量分别为3.09％,3.00％,2.81％,2.84％,而Mg2Ni的吸氢量则只有2.60％.随着B含量的增加,含B合金吸氢量略有降低;在含B的试样中,含5％B的合金吸氢速率最大,仅需180 s便能完成吸氢.所有含B合金的放氢平台均较Mg2Ni高且较为平坦.本次实验表明,B的添加量对合金性能的提升存在一个最优值,本次实验结果显示,添加5％B相对较好地改善合金的储氢性能,提高合金吸氢量和放氢平台压的同时能保持较快的吸氢速率.     

Phase forming law and electrochemical properties of A2B7-type La-Y-Ni-based hydrogen storage alloys with different La/Y ratios

The effects of different proportions of La and Y elements in the A-side on the structure and properties of A₂B₇-type La-Y-Ni hydrogen storage alloys were investigated.The(La,Y)₂Ni₇ hydrogen storage alloys with different La/Y ratios were prepared by sintering the Y₂Ni₄ precursor and different AB₅-type precursors at 1298 K for 5 h and subsequently annealed for 20 h at 1248 K.All the alloys only contain Ce₂Ni     

Highly ameliorated gaseous and electrochemical hydrogen storage dynamics of nanocrystalline and amorphous LaMg12-type alloys prepared by mechanical milling

Nanocrystalline and amorphous LaMg12-type alloy-Ni composites with a nominal composition of LaMg11 Ni+x wt.% Ni (x=100, 200) were synthesized via ball milling.The influences of ball mill-ing duration and Ni adding amount x on the gaseous and electrochemical hydrogen storage dynamics of the alloys were systematically studied.Gaseous hydrogen storage performances were studied by a differential scanning calorimeter and a Sievert apparatus.The dehydrogenation activation energy of the alloy hydrides was evaluated by Kissinger method.The electrochemical hydrogen storage dynam-ics of the alloys was investigated by an automatic galvanostatic system.The H atom diffusion and ap-parent activation enthalpy of the alloys were calculated.The results demonstrate that a variation in Ni content remarkably enhances the gaseous and electrochemical hydrogen storage dynamics perform-ance of the alloys.The gaseous hydriding rate and high-rate discharge (HRD) ability of the alloys ex-hibit maximum values with varying milling duration.However, the dehydriding kinetics of the alloys is always accelerated by prolonging milling duration.Specifically, rising milling time from 5 to 60 h makes the hydrogen desorption ratio (a ratio of the dehydrogenation amount in 20 min to the saturat-ed hydrogenation amount) increase from 57% to 66% for x=100 alloy and from 57% to 70% for x=200.Moreover, the improvement of gaseous hydrogen storage kinetics is attributed to the descending of dehydrogenation activation energy caused by the prolonging of milling duration and growing of Ni content.     

快淬纳米晶/非晶Mg2-xLaxNi (x=0～0.6)合金的贮氢动力学

为了改善Mg2Ni型合金气态及电化学贮氢动力学性能,用La部分替代合金中的Mg,用快淬技术制备了Mg2-xLaxNi(x=0,0.2,0.4,0.6)合金,用XRD,SEM,HRTEM分析了铸态及快淬态合金的微观结构;用自动控制的Sieverts设备测试了合金的气态贮氢动力学性能,用程控电池测试仪测试了合金的电化学贮氢动力学.结果发现,快淬无La合金具有典型的纳米晶结构,而快淬含La合金显示了以非晶相为主的结构,表明La替代Mg提高Mg2Ni型合金的非晶形成能力.La替代Mg明显地改变Mg2Ni型合金的相组成.当La替代量x=0.4时,合金的主相改变为(La,Mg) Ni3+ LaMg3.合金的气态及电化学吸放氢动力学对La含量及快淬工艺敏感,La替代使合金的吸氢动力学降低,但适量的La替代可以明显改善合金的放氢动力学及高倍率放电能力.适当的快淬处理可以提高合金的气态及电化学贮氢动力学,但获得最佳贮氢动力学的快淬工艺与合金的成分密切相关.     

Phase structure and hydrogen storage properties of REMg8.35Ni2.18Al0.21 （RE=La, Ce, Pr, and Nd） hydrogen storage alloys

REMg 8.35Ni2.18Al0.21 (RE=La, Ce, Pr, and Nd) alloys were prepared by induction melting and following annealing. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results showed that the alloys were composed of Mg2Ni, (La, Pr, Nd)Mg2Ni, (La, Ce)2Mg17 , (Ce, Pr, Nd)Mg12 and Ce2Ni7 phases. The above phases were disproportioned into Mg2NiH4 , MgH2 and REH x (x=2.51 or 3) phases in hydriding. CeH2.51 phase transformed into CeH2.29 phase in dehydriding, whereas LaH3 , PrH3 and NdH3 phases remained unchanged. The PrMg8.41Ni2.14Al0.20 alloy had the fastest hydriding kinetics and the highest dehydriding plateau pressure while the CeMg8.35Ni2.18Al0.21 alloy presented the best hydriding/dehydriding reversibility. The onset hydrogen desorption temperature of the CeMg8.35Ni2.18Al0.21 hydride decreased remarkably owing to the phase transformation between the CeH2.51 and the CeH2.29 .     

Effect of annealing treatment on hydrogen storage properties of La-Ti-Mg-Ni-based alloy

The present study dealt with investigations on the effects of annealing on the hydrogen storage properties of La 1.6 Ti 0.4 MgNi 9 alloys.The experimental alloys were prepared by magnetic levitation melting followed by annealing treatment.For La 1.6 Ti 0.4 MgNi 9 alloys,LaNi 5,LaNi 3 and LaMg 2 Ni 9 were the main phases,Ti 2 Ni phase appeared at 900℃.Annealing not only enhanced the maximum and effective hydrogen storage capacity,improved the hydrogen absorption/desorption kinetics,but also increased the discharge capacity.The cyclic stability had been improved markedly by annealing,e.g.,when the discharge capacity reduced to 60% of maximum discharge capacity,the charge/discharge cycles increased from 66(as-cast) to 89(annealed at 800℃) and 127 times(annealed at 900℃).La 1.6 Ti 0.4 MgNi 9 alloy annealed at 900℃ exhibited better electrochemical properties compared to the other two alloy electrodes.     

Microstructures and hydrogen storage properties of as-cast and copper-mould-cast LaMg4Ni alloys

Phase compositions, morphologies and hydrogen storage properties of the as-cast and copper-mould-cast LaMgaNi alloys were studied. The dehydriding onset temperature of the as-cast alloy hydride was about 500 K, which was at least 50 K higher than that of the copper-mould-cast one, and the copper-mould-cast alloy hydride had a faster dehydriding rate compared with as-cast one. Additionally, the copper-mould-cast alloy could uptake 2.85 wt.% hydrogen, which was 95.0% of saturated hydrogen storage capac- ity at room temperature. While only 1.80 wt.% hydrogen （60% of saturated capacity） was absorbed for the as-cast alloy under the same conditions. The reversible hydrogen storage capacities and plateau hydrogen pressures of the two alloys were close. X-ray dif- fractions and scanning electron microscopy results indicated that similar thermodynamic property of the two alloys should be ascribed to the same hydrogen storage phase, Mg and MgzNi. The better hydrogen sorption kinetics of copper-mould-cast alloy should be as- cribed to the more uniform phase distribution compared with that of the as-cast one.     

Influence of lanthanon hydride catalysts on hydrogen storage properties of sodium alanates

NaAlH4 complex hydrides doped with lanthanon hydrides were prepared by hydrogenation of the ball-milled NaH/Al+ xmol.% RE-H composites (RE=La,Ce;x=2,4,6) using NaH and Al powder as raw materials. The influence of lanthanon hydride catalysts on the hydriding and dehydriding behaviors of the as-synthesized composites were investigated. It was found that the composite doped with 2 mol.% LaH3.01 displayed the highest hydrogen absorption capacity of 4.78 wt.% and desorption capacity of 4.66 wt.%, respectively. Moreover, the composite doped with 6 mol% CeH 2.51 showed the best hydriding/dehydriding reaction kinetics. The proposed catalytic mechanism for reversible hydrogen storage properties of the composite was attributed to the presence of active LaH3.01 and CeH2.51 particles, which were scattering on the surface of NaH and Al particles, acting as the catalytic active sites for hydrogen diffusion and playing an important catalytic role in the improved hydriding/dehydriding reaction.     

Hydriding/dehydriding behaviors of La2Mg17-10 wt.%Ni composite prepared by mechanical milling

The structure and hydriding/dehydriding behaviors of La2Mg17-10 wt.%Ni composite prepared by mechanical milling were investigated. Compared with the un-milled sample, the as-milled alloys were ready to be activated and the kinetics of hydrogen absorption was relatively fast even at environmental temperature. The composite milled for 10 h absorbed 3.16 wt.% hydrogen within 100 s at 290 K. The kinetic mechanisms of hydriding/dehydriding reactions were analyzed by using a new model. The results showed that hydrogenation processes for all composites were controlled by hydrogen diffusion and the minimum activation energy was 15.3 kJ/mol H2 for the composite milled for 10 h. Mechanical milling changed the dehydriding reaction rate-controlling step from surface penetration to diffusion and reduced the activation energy from 204.6 to 87.4 kJ/mol H2. The optimum milled duration was 5 h for desorption in our trials.     

A comparison study of hydrogen storage performances of SmMg11Ni 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.     

Effect of praseodymium substitution for lanthanum on structure and properties of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1（X=0.00-0.20） hydrogen storage alloys

In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system (AB3.5-type) hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1(x=0, 0.10, 0.15, 0.2) hydrogen storage alloys were prepared. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) analyses revealed that two alloys (x=0.0 and 0.10) were composed of (La, Mg)2(Ni,Al)7 phase, La(Ni,Al)5 phase and (La,Mg)Ni2 phase, while other alloys (x=0.15 and 0.20) consisted of (La,Mg)2(Ni,Al)7 phase, La(Ni,Al)5 phase, (La,Mg)Ni2 phase and (La, Mg)(Ni,Al)3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Elec-trochemical studies showed that the discharge capacity decreased from 360 mAh/g (x=0.00) to 335 mAh/g (x=0.20) as x increased. But the high-rate dischargeability (HRD) of alloy electrodes increased from 26% (x=0.00) to 56% (x=0.20) at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.     

Structure and electrochemical hydrogen storage characteristics of the as-cast and annealed La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 （x=0-0.4） alloys

In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4) elec-trode alloys were fabricated by casting and annealing. The microstructures of the as-cast and annealed alloys were characterized by XRD and SEM. The electrochemical hydrogen storage characteristics of the as-cast and annealed alloys were measured. The results revealed that all of the experimental alloys mainly consisted of two phases: (La,Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. As Sm content grew from 0 to 0.4, the discharge capacity and the high rate discharge ability (HRD) first in-creased and then decreased for the as-cast and annealed alloys, whereas the capacity retaining rate (S100) after 100 cycles increased continuously.