Phase structure and hydrogen storage properties of LaMg3.93Ni0.21 alloy

The phase structure and hydrogen storage property of LaMg3.93Ni0.21 alloy were studied.XRD and SEM results exhibited that LaMg3.93Ni0.21 alloy consisted mainly of LaMg3,La2Mg17 and LaMg2Ni phases;after hydriding/dehydriding process,all the three phases transformed,La3H7 phase existed and the actual hydrogen absorption phases were Mg and Mg2Ni phases.Pressure-composition-temperature (P-C-T)measurement showed that the reversible hydrogen storage capacity of LaMg3.93Ni0.21 alloy was 2.63 wt.%,and the absorption time for reaching 90%of the storage capacity was 124 s at 523 K,and it was 1850 s for deabsorbing 90%of the maximum dehydrogen capacity.The hydriding process of LaMg3.93Ni0.21 alloy followed the nucleation and growth mechanisms.The enthalpy and entropy for hydriding and dehydriding reactions of the Mg phase in LaMg3.93Ni0.21 alloy were calculated to be-66.38±1.10 kJ/mol H2,-100.96±1.96 J/(K·mol)H2 and 68.50±3.87 kJ/mol H2,98.28±5.48 J/(K·mol)H2,respectively.A comparison of these data with those of MgH2(-74.50 kJ/mol H2,-132.30 J/K·mol H2)suggested that the hydride of LaMg3.93Ni0.21 alloy was less stable than MgH2.The existence of La hydride and synergetic effect of multiphase led to higher reversible hydrogen storage capacity and better kinetic property at lower temperature for LaMg3.93Ni0.21 alloy.     

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.     

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.     

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 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 .     

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     

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.     

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.     

Effects of annealing on microstructures and electrochemical properties of La0.8Mg0.2Ni2.4Mn0.10Co0.55Al0.10 alloy

The La0.8Mg0.2Ni2.4Mn0.10Co0.55Al0.10 alloy was prepared by induction melting. The structural and morphological characterizations were performed by means of X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical measurements were performed using LAND and CHI 660b electrochemical workstation. The main phases of the alloy were LaNi5 and (La,Mg)Ni3. After annealing, the maximum discharge capacity, cycle stability and high rate dischargeability (HRD) were improved obviously. The maximum discharge capacity reached 373.80 mAh/g (T=1173 K), the C100/Cmax(%) was 72.63% (T=1173 K), and the value of HRD reached 51.8% at a discharge current density of 1150 mA/g (T=1173 K). The cyclic voltammetry (CV) and potentiodynamic polarization were also studied.     

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.     

Hydrogen Storage Properties of Graphite-Modified Mg-Ni-Ce Composites Prepared by Mechanical Milling Followed by Microwave Sintering

The Mg₁₇Ni_1.5Ce_0.5 hydrogen storage composites with different contents of graphite were prepared by a new method of mechanical milling and subsequent microwave sintering. The small particle size (~25 ??m) and the low echo ratio of power indicate that graphite plays an important role not only as a lubricant during mechanical milling but also as a supplementary heating material during microwave sintering. As a catalyst in the hydriding/dehydriding (H/D) reaction, graphite also improved the hydrogen storage properties of the composites. The hydrogen absorption and desorption capacities of Mg₁₇Ni_1.5Ce_0.5 with 5 wt pct graphite were 5.34 and 5.30 wt pct H₂ at 573 K (300 °C), its onset temperature of dehydriding reaction was 511 K (238 °C), and its activation energies of H/D reaction were 40.9 and 54.5 kJ/mol H₂, respectively. The kinetic mechanisms of the H/D reaction are also discussed.     

制备工艺对La_(0.80)Mg_(0.20)Ni_(3.75)合金电极性能的影响

采用中频感应真空熔炼(IM)和放电等离子烧结(SPS)工艺制备La0.80Mg0.20Ni3.75合金。XRD分析表明,这两种工艺制备的合金均含有LaNi5和(La,Mg)2Ni7主相,而中频感应真空熔炼法制备的合金(IMLa合金)还含有(La,Mg)Ni3相,放电等离子烧结法制备的合金(SPSLa合金)还含有Ni及La2Mg17相。电化学性能测试结果表明,作为镍氢电池负极材料,IMLa合金的放电容量、损耗角及极限电流密度均较大;而SPSLa合金的循环性能较好,这归因于SPSLa合金晶粒细小,组织均匀,Ni和La2Mg17相弥散分布,可减弱其电极脱落程度。     

Co含量对La0.55Pr0.05Nd0.15Mg0.25Ni3.5-xCoxAl0.25（x=0～0.4）储氢合金电极性能的影响

采用电磁感应悬浮炉制备La0.55Pr0.05Nd0.15Mg0.25Ni3.5-xCoxAl0.25(x=0,0.1,0.2,0.3,0.4)系列合金,研究Co含量对合金的相结构、吸放氢性能和电化学性能的影响。研究结果表明,该系列合金主要由LaNi5、Nd2Ni7相组成。当Co含量大于0.2时,合金中出现La2Ni7相。压强-吸氢量-温度(Pressure-Content-Temprature)测试显示在303 K温度下,合金具有良好的吸氢性能,当x=0.4时合金的最大吸氢量为1.29(质量分数,%)。电化学测试表明:随x值变化,合金电极的最大放电容量分别为340.0(x=0.0)、346.6(x=0.1)、370.0(x=0.2)、320.0(x=0.3)和346.6(mA.h)/g(x=0.4);随Co含量增加,合金电极容量保持率不断增加,高倍率放电性能先增加后减小,循环伏安曲线、氢在合金体中的扩散系数D共同反映了合金电极的动力学特性。     

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.     

氢化燃烧法合成镁基储氢合金进展

以Mg2 Ni为例系统综述了氢化燃烧法制备镁基储氢合金的进展 ,包括其工作原理 ,氢化燃烧法和其它制备镁基储氢合金方法的比较 ,影响氢化燃烧的因素以及材料的氢化特性。较为详细地介绍了国内外的研究状况并进行比较 ,通过比较Mg2 Ni、Mg2 FeH6 、Mg2 CoH5等储氢合金的吸氢性能 ,指出制备镁基储氢合金的理想发展方向应该是采用复合方法获得实用产品 ,即结合氢化燃烧 ,机械合金化 ,多元化 ,纳米化等方法 ,制备非晶态合金 ,以期达到低温下吸放氢量大于 5 %(质量分数 ) ,具有良好的动力学性能 ,使用寿命长 ,低价格的效果。     

Effect of annealing temperature on microstructure and electrochemical performance of La0.75Mg0.25Ni3.5Co0.2 hydrogen storage electrode alloy

To improve the cyclic stability of La-Mg-Ni system alloy, as-cast La0.75Mg0.25Ni3.5Co0.2 alloy was annealed at 1123, 1223, and 1323 K for 10 h in 0.3 MPa argon. The microstructure and electrochemical performance of different annealed alloys were investigated systematically by X-Ray Diffraction （XRD）, Scanning Electron Microscopy （SEM）, X-Ray Photoelectron Spectroscopy （XPS）, and electrochemical experiments. The results obtained by XRD and SEM showed that the as-cast and annealed （1123 K） alloys had multiphase structure containing LaNis, （La, Mg）2（Ni, Co）7 and few LaNi2 phases. When annealing temperatures approached 1223 and 1323 K, LaNi2 phase disappeared. The annealed alloys at 1223 and 1323 K were composed of LaNi5, （La, Mg）2（Ni, Co）7 and （La, Mg）（Ni, Co）3 phases. With increasing annealing temperature, the maximum discharge capacity of the alloy decreased monotonously, but the cyclic stability was improved owing to structure homogeneity and grain growth after annealing, as well as the enhancement of anti-oxidation/corrosion ability and the suppression of pulverization during cycling in KOH electrolyte.     

Influence of elemental composition on crystal structure and hydrogen storage performance for Mg-containing alloys

The influence of elemental composition on the crystal structure, hydrogen storage and electrochemical properties for Mg-containing alloys was investigated. As La/Mg ratio decreased, the slight change of Ni content was detected. XRD results indicated that these alloys were composed of LaNi 5 and Mg-containing phases. The lattice parameters of Mg-containing phases decreased. Meanwhile, the mass fraction of Mg-containing phases varied with the change of La/Mg and Ni. The hydrogen storage capacity reached ～1.6 wt.% for La/Mg≧ 3 :1 and decreased to ～0.71 wt.% for La/Mg=1. Two hydrogen absorption processes were observed because of the existence of the multiphases for La/Mg≧ 3 :1. With decreasing La/Mg ratio, the equilibrium pressurerose due to the shrinkage of the lattice parameter. Meanwhile, one hydrogen absorption process was obviously present. The discharge capacity of these as-cast alloys was higher, but the cyclic stability was poor for La/Mg≧ 3 :1 due to the partial amorphisation. It was better for La/Mg≤2 although the discharge capacity was lower. The polarization resistance increased, contrarily the exchange current density decreased with decreasing Mg content.     

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 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.     

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.