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.

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.

Phase Structure and Cycle Stabilities of Mg_2Ni/Mm_(0.3)Ml_(0.7)Ni_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) Composite Hydrogen Storage Alloys Prepared by Two-step re-melting

Mm0.3Ml0.7Ni3.55Co0.75Mn0.4-Al0.3 alloy has high chemical activity and favorable plateaus pressure. Mg2Ni is in favor of high hydrogen storage capacity and low weight, but it is difficult to be activated. In order to improve the capacity and cycle performances of hydrogen-storage alloy electrodes, Mm0.3Ml0.7Ni3.55Co0.75Mn0.4-Al0.3-x%Mg2Ni(x=0, 5, 10, 30) composite hydrogen storage alloys prepared by two-step re-melting were investigated in this work. The influences of Mg2Ni content on the cycle stabilities were analyzed by electrochemical methods. It was observed by XRD that the main phase of all the alloys is LaNi5 and the crystal lattice parameters of LaNi5 are changed with the increasing of x value, i.e, a-axis and unit cell volume decrease and c-axis decreases nonlinearly. The c-axis of alloy with x=5 is larger than the others. With the increasing of x value, capacity retentions of the composite hydrogen storage alloys rise from 66.21% while x=0 to 82.04% while x=10, but the capacity retention of the composite alloy with 30% Mg2Ni declines because of its decreasing axial ratio. More over, the composite alloy with 5% Mg2Ni shows the best cycle stability and higher discharge capacity, and it is an appropriate candidate for battery materials.

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.

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

Phase Structure and Electrochemical Characteristics of Ml(Ni_(3.55)Co_(0.75)Mn_(0.40)Al_(0.30))_(5x)(x=0.88,0.92,0.96,1.00) Hydrogen Storage Alloys

The phase structure and electrochemical characteristics of Ml （（Ni3.55Co0.75Mn0.40Al0.30）sx （ x = 0.88, 0.92, 0.96, 1.00） hydrogen storage alloys were studied. The effect of the stoichiometric ratio on the phase structure and electrochemical characteristics was analyzed. The results of XRD reveal that all the alloys consist mainly of LaNi5 phase with the hexagonal CaCu5 structure. But a few of the diffraction peaks of La2Ni7 phase on XRD pattern are observed when x ≤ 0.92, and with decreasing x, the intensity of La2Ni7 diffraction peaks increases and the values of lattice parameters a and cell volume increase, c and c/a of LaNi5 phase decrease gradually. When x≥0.96, La2Ni7 phase disappears and the alloys become single CaCu5-type. The electrochemical tests show that the maximum discharge capacity, high rate dischargeability and low temperature dischargeability are improved to different degrees by adjusting the stoichiometric ratio.

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%.

Effects of chemical coating with Ni on electrochemical properties of Mg_2Ni hydrogen storage alloys

The effects of nickel coating on the electrochemical properties of Mg2Ni hydrogen storage alloys are presented in this paper. X-ray diffraction （XRD） and scanning electron microscope （SEM） techniques were employed to examine the crystal structure and surface morphologies of the bare and Ni-coated Mg2Ni alloys. The electrochemical properties of alloys were characterized by cyclic voltammetry （CV） and dectrochemical impedance spectroscopy （EIS）. The results showed that Ni coating not only decreased the charge transfer resistance, but also decreased the H atom diffusion resistance for Mg2Ni alloys. It was also found that Ni coating effectively improved the discharge capacity, but decreased the cycling performance of the as-synthesized Ni-coated MgzNi alloys. The discharge current has a great impact on the cycling perform- ance of the as-synthesized Ni-coated Mg2Ni alloys.

Electrochemical characteristics of amorphous MgTi_xNi(x = 0,0.1,and 0.2) hydrogen storage alloys

MgTixNi （x = 0, 0.1, and 0.2） alloys were successfully prepared by mechanical alloying （MA）, and the influence of milling time on the electrochemical characteristics of the electrodes was discussed. MgTixNi alloys after 90 h milling displayed the best electrochemical performance The X-ray diffraction patterns showed that the alloy ball-milled for 90 h was amorphous with a widened diffraction peak. The charge-discharge tests indicated that these alloys had good electrochemical activation properties, and the MgTi0.2Ni alloy electrode exhibited the best cycle performance. The initial discharge capacity of the MgTi0.2Ni alloy reached up to 401.1 mAh·g^-1, and the retention rate of capacity was 31.0% after 30 cycles, much higher than that of MgNi （17.3%）. The Tafel polarization curves revealed that Ti addition could enhance the anticorrosion performance of these alloys in alkali solution, which was responsible for the ameliorated cyclic stability of these alloy electrodes.

Effect of Rapid Quenching on Electrochemical Properties of AB_5 and AB_(3.5)-Type Hydrogen Storage Alloys

Effect of rapid quenching on the electrochemical properties of AB5 and AB3.5-type hydrogen storage alloys was studied. The results indicated that the discharge capacities of the rapid quenching MmNi3.55Co0.75Mn0.4Al0.3 alloys decrease under 25 and -35 ℃ with the increase of the quenching rate. Comparatively, the decrease extent of the quenching alloys at -35 ℃ is lower than that at 25 ℃. The result on the study of the cycle life indicated that the quenching process was favorable to improve the cycle stabilities of the MmNi3.55Co0.75-Mn0.4Al0.3 alloys under 25 and -35 ℃. Whereas, the effect of the quenching process on the La0.7Mg0.3(Ni0.85Co0.15)3.5 alloy was different at 25 ℃ from at -35 ℃. Under 25 ℃, the cycle life of the alloy was obviously improved by the quenching process, however, the quenching process did not improve but decreased slightly the cycle life at -35 ℃.

Development of Rare Earth Hydrogen Storage Alloys: Correlation Between Structure, Stability, and Hydrating Properties

The structure of β-LaNi2Hx is mentioned. Special emphasis is laid on the influence of substitutions with metallic elements on the thermodynamic properties of the rare-earth-nickel hydrogen storage alloys. The models of the heat of hydride formation are studied attentively. The relation between the stability and the heat of formation of intermetallic compounds including with other physical properties is discussed. The relations between hydriding properties and the geometric and electronic structure of the intermetallic compounds are presented.

Trends of Chinese RE Hydrogen Storage Alloys

I . Status of Chinese RE Hydrogen Storage Alloys 1. R & D of RE Hydrogen Storage Alloys in China AB5 hydrogen storage materials, taking rare earth mischmetals as raw materials, developed rapidly in China in recent years. Today, different countries attach importance to the development and application of the new

Effect of praseodymium substitution for lanthanum on structure and properties of La_(0.65-x)Pr_xNd_(0.12)Mg_(0.23)Ni_(3.4)Al_(0.1)(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,A1）5 phase and （La,Mg）Ni2 phase, while other alloys （x=0.15 and 0.20） consisted of （La,Mg）2（Ni,A1）7 phase, La（Ni,A1）5 phase, （La,Mg）Ni2 phase and （La,Mg）（Ni,A1）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. Electrochemical 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.

Study on High Rate Discharge Performance and Mechanism of AB_5 Type Hydrogen Storage Alloys

The effects of surface treatment, particle size distribution,rare earth composition and B additive on the high rate discharge performance of hydrogen storage alloys were investigated. It is found that the activity, discharge capacity and high rate dischargeability of the alloys are improved after physical and chemical modification as a result of the increase of the surface area and formation of the electrocatalysis layers, which increase both the electrochemical reaction rate on the alloy surface and H diffusion rate in the alloy bulk. It is also found that both the over-coarse and over-fine particle size increase the contact resistance of the electrode, resulting in a decrease of discharge capacity, deterioration of high rate dischargeability and lower discharge plateau. In another word, a suitable particle size distribution can enhance the alloy activity, discharge capacity and high rate dischargeability. In addition, the high rate dischargeability is enhanced by increasing La content and decreasing Ce content of the alloy composition because of enlargement of the unit cell volume and the improvement of the surface activity. Moreover, B additive resultes in the formation of the second phase, and makes the alloys easier pulverization, which greatly improves the activity, discharge capacity and high rate dischargeability.

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.

Research of heat treatment of low-Co AB_5 type hydrogen storage alloys for MH-Ni batteries

The effects of low-Co AB_5 type hydrogen storage alloys prepared by quenchingand annealing on the performances of MH-Ni batteries were investigated, and the characteristics ofthe low-Co AB_5 type hydrogen storage alloys were compared with those of the high-Co AB_5 typehydrogen storage alloy as well. The results showed that the faster the cooling of the low-Cohydrogen storage alloy is, the better homogeneity of the chemical composition for the alloy and thelonger cycle life of the battery are, but the electrochemical discharge capacity and high-ratedischarge ability are reduced. The high-rate discharge ability and charge retention of MH-Nibatteries for the conventional as-cast annealed low-Co hydrogen storage alloy were superior to thosefor the rapidly quenched low-Co hydrogen storage alloy and the high-Co hydrogen storage alloy, buta little inferior in the cycle life.

Hydrogen Storage Properties of Ti_(1.2)Fe+xCa Hydrogen Storage Alloys

The hydrogen storage properties of Ti1.2Fe+xCa (x=1%, 3% and 5% in mass fraction) alloys was investigated. Results stow that the modified alloys can be activated without any thermal treatment at room temperature due to the addition of Ca and excess Ti in (lie alloys. Hydrogen storage properties of these modified alloys vary with Ca amount and reaction temperature. In addition, the influence mechanism of the addition of Ca and excessive Ti on the activation behavior and hydrogen storage capacity of the alloys was discussed.

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.