Structure and Electrochemical Properties of A_2B_7-Type La-Mg-Ni Hydrogen Storage Alloys

Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is great, resulting in a linear decrease of the unit cell parameters of main phases and increase of hydrogen absorption/desorption plateau as Mg content increases. Electrochemical measurements show that as the Mg content increases, the discharge capacity of alloy electrodes first increases and then decreases. The cyclic stability presents a deteriorative trend. La1.4Mg0.6 Ni7 alloy electrode exhibits the maximum electrochemical discharge capacity （378 mAh·g^-1）, and the La1.6Mg0.4Ni7 alloy electrode shows the best cyclic stability （S270 = 81%）.

Structure and electrochemical properties of La-Mg-Ni system hydrogen storage alloys with different Co contents

The structure and electrochemical properties of the La0.7Mg0.3Ni3.4-xMn0.1Cox （x=01.05） hydrogen storage alloys were investigated. The crystal structure and the lattice parameters of the alloys were analyzed by X-ray diffractometry and Rietveld method. Electrochemical properties of the alloys including p—c—t curves, discharge capacity, discharge capacity retention were studied. The results show that （La, Mg）Ni3 and LaNi5 are the main phases of all the alloys. The plateau pressure for hydrogen absorption/desorption decreases and the hydrogen storage capacity firstly increases and subsequently decreases with increasing Co content. The values of the maximum discharge capacity of the alloy electrodes remain in range of 395.3403.1mA·h/g in spite of the change of Co content. The cycling stability of the alloy electrodes is greatly improved with increasing Co content, which is attributed to the suppression of the cell volume expansion during hydriding, leading the pulverization of the alloy particles lowered and the oxidation/corrosion of the active elements reduced.

Effects of annealing treatment on the microstructure and electrochemical properties of low-Co hydrogen storage alloys containing Cu and Fe

The effects of annealing treatment on the microstructure and electrochemical properties of low-Co LaNi 3.55 Mn 0.35 Co 0.20 Al 0.20 Cu 0.75 Fe 0.10 hydrogen storage alloys were investigated. X-ray diffraction （XRD） analysis indicated that annealing treatment remarkably reduced the lattice strain and defects, and increased the unit-cell volume. The optical microscope analysis showed that the as-cast alloy had a crass dendrite microstructure with noticeable composition segregation, which gradually disappeared with increasing annealing temperature, and the micro-structure changed to an equiaxed structure after annealing the alloy at 1233 K. The electrochemical tests indicated that the annealed alloys demonstrated much better cycling stability compared with the as-cast one. The capacity retention at the 100th cycle increased from 90.0% （as-cast） to 94.7% （1273 K）. The annealing treatment also improved the discharge capacity. However, the high rate dischargeability （HRD） value of the annealed alloy slightly dropped, which was believed to be ascribed to the decreased exchange current density and the hydrogen diffusion coefficient in alloy bulk.

Effects of Strip Casting and Annealing on Electrochemical Properties of LPCNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) Hydrogen Storage Alloys

The effect of thickness (1 similar to 10 mm) of the ingots on the electrochemical properties of as-cast and annealed strip cast LPCNi3.55Co0.75Mn0.4Al0.3 hydrogen storage alloys was investigated. It is found that the 0.2 C discharge capacity of as-cast LPCNi3.55Co0.75Mn0.4Al0.3 alloy increases with the increase of the thickness of the ingots. As-east alloy with the thickness of 10 mm shows better activation property, higher 1C discharge capacity and better cyclic stability than others. It is mainly contributed to its larger unit cell volume and less internal stress. Annealed LPCNi3.55Co0.75Mn0.4Al0.3 alloy with the thickness of 3 mm shows much better comprehensive electrochemical properties than as-east one; The cyclic. stability of the alloy with the thickness of 6 mm and the activation properties of the alloys with the thickness of 3 similar to 6 mm are improved after annealing. It is mainly owing to the great release of internal stress and the decrease of the segregation of Mn in the alloys.

Effect of Ni,Fe and Fe-Ni alloy catalysts on the synthesis of metal contained carbon nano-onions and studies of their electrochemical hydrogen storage properties

Three types of carbon nano-onions（CNOs） including Ni@CNOs.Fe3C@CNOs and Fe0.64Ni0.36@CNOs nanoparticles have been synthesized by catalytic decomposition of methane at 850 ℃ using nickel,iron and iron-nickel alloy catalysts.Comparative and systematic studies have been carried out on the morphology,structural characteristics and graphitic crystallinity of these CNOs products.Furthermore,the electrochemical hydrogen storage properties of three types of CNOs have been investigated.Measurements show that the Ni@CNOs have the highest discharge capacity of 387.2 mAh/g,coiTesponding to a hydrogen storage of 1.42%.This comparison study shows the advantages of each catalyst in the growth of CNOs.enabling the controllable synthesis and tuning the properties of CNOs by mediating different metals and their alloy for using in the fuel cell system.

Microstructure and electrochemical properties of LaNi_(4-x)FeMn_x (x=0-0.8) hydrogen storage alloys

In order to reduce the cost of LaNi5 based hydrogen storage alloys, effect of substitution of Mn for Ni on structural and electrochemical properties of LaNi4-xFeMnx (x=0-0.8) hydrogen storage alloys was studied systematically. X-ray diffraction (XRD) and scanning electron microscope (SEM) showed that LaNi5 and La2Ni7 phases were invariably present in all alloy samples, and when x >= 0.4, (Fe, Ni) phase was observed. Electrochemical studies revealed that the discharge capacity reached a maximum value of 306.4 mAh/g when x=0.2 and the cycling stability decreased with the increase of x. With the increase of Mn content, hydrogen diffusion coefficient decreased, whereas high rate discharge-ability (HRD) and exchange current density first increased slowly when x <= 0.2 and then decreased markedly when x=0.8, indicating that electrochemical reaction on the surface of alloy electrodes had strong influence on kinetic property.

Microstructure and electrochemical properties of melt-spun Nd_(0.8)Mg_(0.2)(Ni_(0.8)Co_(0.2))_(3.8) hydrogen storage alloy

The effects of rapid solidification on the microstructure and electrochemical properties of Nd0.8Mg0.2(Ni0.8Co0.2)3.8 alloy were systematically investigated.The microstructure of alloys was characterized by scanning electron microscopy(SEM),X-ray diffractometer(XRD) and transmission electron microscopy(TEM).It was found that the melt-spun Nd0.8Mg0.2(Ni0.8Co0.2)3.8 ribbons became thinner and the average grain size of the ribbons became smaller with increasing wheel speed.A fraction of amorphous phase was obs...

CRYSTAL STRUCTURE AND ELECTROCHEMICAL PROPERTIES OF Zr(Mn_(1-x)Ni_x)_2(0.40≤x≤0.75) HYDROGEN STORAGE ALLOYS

The crystal structure, phase abundance and the electrochemical properties of Zr(Mn1-x Nix)2 (0.40 ≤x≤0.75) alloys were investigated by means of XRD, Rietveld refinement method and electrochemical measurements. The alloys are multiphase. C15 Laves phase occurs as a main phase accompanying with C14 phase and other minor phases, indicating that Ni element is C15-stabilized element for ZrMn2 alloy. The phase abundance and lattice parameters of Laves phase are influenced significantly by Ni substitution. The Zr(Mn0.45 Ni0.55)2 alloy with the highest amount of C15 phase exhibits the maximum electrochemical capacity of 242m Ah/g. C14 phase occurring in Zr-Mn-Ni alloys is beneficial for the electrochemical kinetics of hydride electrodes.

Electrochemical Properties of Strip Casting LPCNi_(3.55) Co_(0.75) Mn_(0.4) Al_(0.3) Hydrogen Storage Alloys

LPCNi 3.55 Co 0.75 Mn 0.4 Al 0.3 hydrogen storage alloy was investigated, and the effects of thickness of its strip casting ingots(as cast) on the electrochemical performances were discussed. It was found that the 0.2 C discharge capacity increased with the increase of the thickness (from 1 mm to 10 mm) of the ingots, mainly due to the enlargement of the unit cell volume; Among the thickness of the ingots in our study, 10 mm sample showed a better activation property; LPCNi 3.55 Co 0.75 Mn 0.4 Al 0.3 alloy with 10mm showed higher comprehensive properties than those with other thickness under 1C rate.

Phase Structure and Electrochemical Properties of RE-Mg Based Composite Hydrogen Storage Alloys

A new type of AB_5-x%LaMg_3(x=2, 3, 4, 5, 6, 7, 8)composite hydrogen storage alloys were prepared by sintering the powder mixtures of a commercial AB_5 alloy and LaMg_3 alloy. The phase structure and electrochemical characteristics of the composite hydrogen storage alloys were also studied. It is shown that AB_(5)-x%LaMg_3(x=2, 3, 4, 5, 6, 7, 8)composites have mult; phase structure. The matrix phase has CaCu_5 structure, the second phase is LaNi_3 phase. The maximum discharge capacity, discharge capacity at low temperature and HRD of AB_5 alloy electrodes are greatly improved after the composite. The maximum discharge capacity of the composite electrodes increases from 325 mAh·g^(-1) for x=0 to 358 mAh·g^(-1) for x=5, and the HRD of the composites for x=5 at the current density of 1200 mA·g^(-1)30% of that of the alloy at 60 mA·g^(-1). The discharge capacity of AB_5-x%LaMg_3 composite alloy electrode at 233 K is up to 174 mAh·g^(-1). The improvement of the electrochemical characteristics of the composite electrodes seems to be related with formation of the LaNi_3 second phase.

Study on Particle Size and Electrochemical Properties of Rare Earth Based Hydrogen Storage Alloys

The rare earth based hydrogen storage alloys Ml_ 0.7Mm_ 0.3(Ni_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3) were chosen as objects of investigation in this paper. The effects of particle size on electrochemical properties of the alloy were investigated. The results indicate that the alloy with particle size of 100 and 150 mesh shows good activation behavior and high discharge capacity (the first discharge capacity and the maximum discharge capacity), but poor cycling stability, low capacity retention and high discharge capacity rate. The Ml_ 0.7Mm_ 0.3(Ni_ 3.55Co_ 0.75Mn_ 0.4Al_ 0.3) alloy with particle size of 150 mesh shows excellent electrochemical properties.

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.

Effect of CoO Addition on Electrochemical Properties of La0.7Mg0.3 （Ni0. 85 Co0. 15 ） 3.5 Hydrogen- Storage Alloy

In order to improve the cycling stability of La-Mg-Ni-Co hydrogen storage alloys, the La0.7Mg0.3 （Ni0.85Co0.15）3.5 alloy was prepared by inductive melting under argon atmosphere. The effect of additive CoO on electrochemical properties of La0.7Mg0.3（Ni0.85 Co0.15）3.5 alloy, which is used as an electrode material was studied. When the addition of CoO is 5 %, both the discharge capacity at high-, low- and room-tem- perature and charge-discharge cycling stability at room temperature can be significantly improved. Electro- chemical measurements and X-ray diffraction （XRD） analyses suggest that CoO improves the electrochemical properties of the La0.7Mg0.3（Ni0.85Co0.15）3.5 alloy by promoting the electrochemical reaction of another phase in the alloy and by self electrochemical reversible reaction occurring during the charge-discharge process.

Electrochemical properties of TiV-based hydrogen storage alloys

The electrochemical properties of the super-stoichiometric TiV-based hydrogen storage electrode alloys(Ti 0.8Zr 0.2)(V 0.533Mn 0.107Cr 0.16Ni 0.2) x(x=2, 3, 4, 5, 6) were studied. It is found by XRD analysis that all the alloys mainly consist of a C14 Laves phase with hexagonal structure and a V-based solid solution phase with BCC structure. The lattice parameters and the unit cell volumes of the two phases decrease with increasing x. The cycle life, the linear polarization, the anode polarization and the electrochemical impedance spectra of the alloy electrodes were investigated systematically. The overall electrochemical properties of the alloy electrode are found improved greatly as the result of super-stoichiometry and get to the best when x=5.

Microstructure and electrochemical properties of low-temperature hydrogen storage alloy used in Ni/MH batteries

AB5 hydrogen storage alloys La0.54Ce0.28Pr0.18Ni4-xCo0.6Mn0.35Alx(x=0.1,0.2,0.3) were prepared by arc melting method under an Ar atmosphere. The results show that the contents of Ni and Al have obvious influences on the microstructure and electrochemical properties of the alloys. Both the lattice parameters and the cell volumes decrease with decreasing x value. Moreover,the discharge capacity at different temperatures,the high rate discharge property,and the cycling life of the alloy electrode are also in close relationship with the x value. When x value increases from 0.1 to 0.3,the discharge capacities with a discharge current density of 60 mA/g slightly decreases at 25 ℃,but evidently deteriorates at -40 ℃,the high-rate property gravely decreases,and the cycle life of the alloy electrode is improved in some extent. Therefore,it is meaningful to control Al content for the AB5 hydrogen storage alloys used in Ni/MH batteries.

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

Manufacturing Process,Electrochemical Properties and Structures of Ml(NiMnTiCo)_5 Hydrogen Storage Alloys

The electrochemical properties, phase structures and microstructures of Ml(NiMnTiCo) 5 hydrogen storage alloys prepared with different processing methods were investigated by electrochemical measurements, XRD, TEM and EDXRD. The rapid solidification such as melt spinning can effectively improve the cycle stability of the alloy, but it also leads to the decrease of initial activation rate and discharge capacity. Annealing at a moderate temperature can make up for these disadvantages. The variation of electrochemical properties for the same alloy prepared by different processing methods is caused by different phase structures and microstructures.

Effect of Rare Earth Elements on Structure and Electrochemical Properties of PuNi_3-type Hydrogen Storage Alloys

Structure and electrochemical properties of (La, Ce, Pr, Nd)_2MgNi_9 hydrogen storage alloys were investigated through orthogonal design experiments, and the alloys were obtained through induction melting followed by annealing treatment. The structure of main phase in alloys belongs to PuNi_3-type with a space group R3m. Rare earth elements, as a substitute of lanthanum, have a significant effect on phase structure of alloys, elements of cerium and neodymium are beneficial to the formation of Gd_2Co_7-type phase with a space group P 6_3/mmc. Rare earth elements can decrease the unit cell volume of main phase of alloys dramatically, and increase the axis ratio. The results of electrochemical experiment showed that the discharge capacity of alloy electrodes ranged from 342.97 to 380.68 mAh·g -1, and elements of cerium and neodymium can reduce the discharge capacity of alloy electrodes significantly. Compared to the electrode of La_2MgNi_9 alloy, the substitution of lanthanum by rare earth elements did not improve the cyclic stability of alloy electrodes due to the anisotropic structure change of unit cell. While rare-earth elements can improve the high rate dischargeability of alloy electrodes, the high rate dischargeability of alloy electrodes could reach the maximum when the unit cell volume of PuNi_3-type structure was about 0532 nm.

Influences of Ti substitution on the structure and electrochemical properties of Mg_(1-x)Ti_xNi(x=0,0.1, 0.2, and 0.3) hydrogen storage alloys

MgNi-based hydrogen storage alloys Mg1–xTixNi （x = 0, 0.1, 0.2, and 0.3） were prepared by means of mechanical alloying. Mg in the alloy was partially substituted by Ti to improve the cycle stability of the alloys. The effects of the substitution of Ti for Mg on the microstructure and electrochemical performances of the alloys were investigated in detail. The results indicate that the substitution of Ti for Mg obviously decreases the discharge capacity, but it significantly improves their cycle stabilities. The microstructure of the alloys analyzed by X-ray diffraction （XRD） and scanning electron microscopy （SEM） shows that the alloys have a dominatingly amorphous structure. The substitution of Ti for Mg helps to improve the anti-oxidation/corrosion ability of the MgNi alloy but demolishes the electrochemical kinetics of hydrogenation/dehydrogenation. The Mg0.9Ti0.1Ni alloy electrode milled for 80 h exhibits the best integrative capability, which has the maximal discharge capacity of 331.66 mAh/g and the C30/Cmax of 63.65%.

INFLUENCE OF Fe DOPING ON ELECTROCHEMICAL PROPERTIES OF Ml(Ni,Co,Mn,Ti)_5 HYDROGEN STORAGE ALLOY

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