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 electrochemical properties of La_(0.7)Ce_(0.3)Ni_(3.75)Mn_(0.35)Al_(0.15)Cu_(0.75-x)Fe_x hydrogen storage alloys

La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-xFex （x=0-0.20） hydrogen storage alloys were synthesized by induction melting and subsequent annealing treatment, and phase structure and electrochemical characteristics were investigated. All alloys consist of a single LaNi5 phase with CaCu5 structure, and the lattice constant a and the cell volume （V） of the LaNi5 phase increase with increasing x value. The maximum discharge capacity gradually decreases from 319.0 mA？h/g （x=0） to 291.9 mA？h/g （x=0.20） with the increase in x value. The high-rate dischargeability at the discharge current density of 1200 mA/g decreases monotonically from 53.1% （x=0） to 44.2% （x=0.20）. The cycling stability increases with increasing x from 0 to 0.20, which is mainly ascribed to the improvement of the pulverization resistance.

Low-Temperature Hydrogen Storage Alloy and Its Application in Ni-MH Battery

Rare earth compositions, La, Ce and Pr in Mm(NiCoMnAl)(5) hydrogen storage alloy, were arranged by uniform design method. The discharge performances and kinetics parameters including capacity, exchange current density, symmetry factor and hydrogen diffusion coefficient of the alloy at -40degreesC, were tested in standard tri-electrode cell. And linear regression method was used to analyze the effect of rare earth compositions on the performances of hydrogen storage alloys. The results show that the capacities of the alloys are positively correlative to the square of Ce content at -40degreesC and under both 0.4 and 0.2C rate. The kinetics parameters and hydrogen diffusion coefficient indicate that the low-temperature performances of the alloys are mainly controlled by hydrogen diffusion process, and the surface electrochemical reaction affects the low-temperature performances to a certain extent. The low-temperature discharge capacities of the battery were also tested. The results show excellent low-temperature performances. The battery delivers 69.6% of its room-temperature capacity at -40degreesC and 0.2C rate, 77.7% at -40degreesC and 0.4C rate, 59.1% at -45degreesC and 0.2C rate.

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.

Effect of Heat-Treatment Process on Properties of Rare Earth Mg-Based System Hydrogen Storage Alloys with AB_3-Type

The effect of heat-treatment process on the properties of Mm0.8Mg0.2(NiCoAlMn)3.5 hydrogen storage alloy was discussed . The electrochemical properties such as cycling stability, activation property, and the plateau voltage of the alloy which was heat-treated in various temperatures and times had different changes during the cycle process, the optimum heat-treatment conditions of this alloy were determined by this work.

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.

Study on Degradation and Recovery of AB_5-Type Hydrogen Storage Alloy Used in Ni-MH Batteries

The influences of deeply overdischarge on the negative electrode alloy of Ni/MH battery were studied. After overdischarge, La(OH) 3 and Al(OH) 3 are found to form in the negative electrode through XRD analysis. The hydrogen storage alloy powder from spent Ni/MH batteries was recovered by chemical and melting method according to degradation mechanism. The structure of recovered alloy was measured by XRD. The experimental results demonstrate that the alloy structure is CaCu 5 type. The constant current charge/discharge test was carried out to the original alloy and the recovered alloy. It is found that their discharge capacities are almost the same, but the discharge potential of the recovered alloy is higher than that of the original alloy. The results of cyclic lifetime test demonstrate that the capacity degradation of the recovered alloy is slower than that of the original one.

Effect of B and Fe substitution on structure of AB_3-type Co-free hydrogen storage alloy

A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys were characterized by XRD,EDS and SEM to investigate the effects of B and Fe substitution for Ni on material structure.The content of LaMg2Ni9 phase within La0.7Mg0.3Ni3 alloy reaches 37.9% and that of La0.7Mg0.3Ni2.9(FeB)0.1 alloys reduces to 23.58%.Among all samples,ground particles with different shapes correspond to different phases.The major substitution occurs in LaMg2Ni9 phase.Electrochemical tests indicate that substituted alloys have different electrochemical performance,which is affected by phase structures of alloy.The discharge capacity of La0.7Mg0.3Ni3 alloy reaches 337.3 mA·h/g,but La0.7Mg0.3Ni2.9(FeB)0.1 alloy gets better high rate discharge(HRD) performance at the discharge rate of 500 mA/g with a high HRD value of 73.19%.

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.

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.

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.

Low-Co rare-earth-based hydrogen storage alloy

On the basis of typical high Co MI(Lanthanum rich mischmetal) based hydrogen storage alloy, a series oflow Co or Co free alloys have been prepared by means of partial or full replacement of Co by a combination of other elements. The microstructures, p c T (pressure concentration temperature) characteristics and electrochemical propertiesunder different charge discharge conditions of the alloys have been investigated. Compared with the high Co alloy, thelow Co or Co free alloys have the lower hydrogen equilibrium pressure and discharge capacity, but have the nearly samehigh rate and high temperature discharge capability, and better charge discharge cycling stability. The reason is revealedby SEM, XPS and XRD results. \[

Effects of alloying side B on Ti-based AB_2 hydrogen storage alloys

Ti-based AB2-type hydrogen storage alloys are a group of promising materials, which will probably replace the prevalent rare earth-based AB5-type alloys and be adopted as the main cathode materials of nickel-metal hydride （Ni-MH） batteries in the near future. Alloying in side B is a major way to improve the performance of Ti-based AB2-type alloys. Based on recent studies, the effects of alloying elements in side B upon the performance of Ti-based AB2-type hydrogen storage alloys are systematically reviewed here. These performances are divided into two categories, namely PCI characteristics, including hydrogen storage capacity （HSC）, plateau pressure （PP）, pressure hysteresis （PH） and pressure plateau sloping （PPS）, and electrochemical properties, including discharge capacity （DC）, activation property （AP）, cycling stability （CS） and high-rate dischargeability （HRD）. Furthermore, the existing problems in these investigations and some suggestions for future research are proposed.

Effects of Mm(NiCoAlMn)_5 hydrogen storage alloy coated with Ni-Co-P alloy by electroless plating on electrochemical properties of hydride electrodes

The effect of chemical plating with Ni Co P alloy on the properties of MH electrodes is investigated. The results show that the efficiency of storage alloy and the activation of MH electrode have been improved by introducing 1.74% cobalt in the Ni Co P alloy coating. The initial discharge capacity is 208 mAh/g. The maximum discharge capacity gets to 298.5 mAh/g. At the same time the cycle life of MH electrodes is improved. The discharge capacity of MH electrodes coated with Ni Co P is 88% of the maximum discharge capacity after 300 cycles. Whereas the discharge capacity of bare alloy electrodes retains 62% of the maximum capacity after 300 cycles. An increment of discharge capacity is mainly due to the superposition of the oxidation current of Co as well as improved efficiency of microcurrent collection. The effect of Ni Co P alloy coating by electroless plating on the kinetic properties of hydride electrode has been systematically investigated by electrochemical techniques. The results indicate that the kinetic properties of MH electrodes, including exchange current density, limiting current density, have been improved markedly. This improvement of kinetic properties leads to the decrease of the overpotential of anodic and cathodic polarization.

Combined “Gateway” and “Spillover” effects originated from a CeNi_(5) alloy catalyst for hydrogen storage of MgH_(2)

Efficient catalysts enable MgH2 with superior hydrogen storage performance.Herein,we successfully synthesized a catalyst composed of Ce and Ni (i.e.CeNi_(5) alloy) with splendid catalytic action for boosting the hydrogen storage property of magnesium hydride (MgH_(2))The MgH2–5wt%CeNi_(5) composite’s initial hydrogen release temperature was reduced to 174℃ and approximately 6.4wt%H_(2) was released at 275℃ within 10 min.Besides,the dehydrogenation enthalpy of MgH_(2) was slightly decreased by adding CeNi_(5).For hydrogenation,the fully dehydrogenated sample absorbed 4.8wt%H_(2) at a low temperature of 175℃.The hydrogenation apparent activation energy was decreased from(73.60±1.79) to (46.12±7.33) kJ/mol.Microstructure analysis revealed that Mg_(2)Ni/Mg_(2)NiH_(4) and CeH_(2.73) were formed during the process of hydrogen absorption and desorption,exerted combined“Gateway”and“Spillover”effects to reduce the operating temperature and improve the hydrogen storage kinetics of MgH_(2).Our work provides an example of merging“Gateway”and“Spillover”effects in one catalyst and may shed light on designing novel highly-effective catalysts for MgH_(2) in near future.

Electrochemical hydrogen storage characteristics of as-cast and annealed La_(0.8-x)Nd_xMg_(0.2)Ni_(3.15)Co_(0.2)Al_(0.1)Si_(0.05)(x=0-0.4)alloys

The La-Mg-Ni-based A2B7-type La0.8-xNdxMg0.2Ni3.15Co0.2Al0.15 （x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were prepared by casting and annealing. The influences of partial substitution of Nd for La on the structure and electrochemical performance of the as-cast and annealed alloys were investigated. It was found that the experimental alloys consist of two major phases, （La, Mg）2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure, as well as some residual phase LaNi3 and NdNi5. The discharge capacity and high rate discharge ability （HRD） of the as-cast and annealed alloys first increase and then decrease with Nd content growing. The as-cast and annealed alloys （x=0.3） yield the largest discharge capacities of 380.3 and 384.3 mA·h/g, respectively. The electrochemical cycle stability of the as-cast and annealed alloys markedly grows with Nd content rising. As the Nd content increase from 0 to 0.4. The capacity retaining rate （S100） at the 100th charging and discharging cycle increases from 64.98% to 85.17% for the as-cast alloy, and from 76.60% to 96.84% for the as-annealed alloy.

Gaseous sorption and electrochemical properties of rare-earth hydrogen storage alloys and their representative applications： A review of recent progress

The improvement of hydrogen storage materials is a key issue for storage and delivery of hydrogen energy before its potential can be realized. As hydrogen storage media, rare-earth hydrogen storage materials have been systematically studied in order to improve storage capacity, kinetics, thermodynamics and electrochemical performance. In this review, we focus on recent research progress of gaseous sorption and electrochemical hydrogen storage properties of rare-earth alloys and highlight their commercial applications including hydrogen storage tanks and nickel metal hydride batteries. Furthermore, development trend and prospective of rare-earth hydrogen storage materials are discussed.

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.

Phase structure and electrochemical properties of non-stoichiometric La_(0.7)Ce_(0.3)(Ni_(3.65)Cu_(0.75)Mn_(0.35)Al_(0.15)(Fe_(0.43)B_(0.57))_(0.10))_x hydrogen storage alloys

Phase structure and electrochemical characteristics of Co-free La0.7Ce0.3（Ni3.65Cu0.75Mn0.35Al0.15（Fe0.43B0.57）0.10）x （0.90≤x≤1.10） alloys were investigated. When x was 0.90, the alloy was composed of LaNi5, La3Ni13B2 and Ce2Ni7 phases. The Ce2Ni7 phase disappeared, and the abundant of La3Ni13B2 phase decreased when x increased to 0.95. When x was 1.00 or higher the alloys consisted of LaNi5 phase. The lattice parameter a and the cell volume V of the LaNi5 phase decreased, and the c/a ratio of the LaNi5 phase increased with x value increasing. Maximum discharge capacity of the alloy electrodes first increased and then decreased with x value increasing from 0.90 to 1.10, and the highest value was obtained when x was 1.00. High-rate dischargeability at the discharge current density of 1200 mA/g increased from 50.7% （x= 0.90） to 64.1% （x=1.10）. Both the charge-transfer reaction at the electrode/electrolyte interface and the hydrogen diffusion in the alloy were responsible for the high-rate dischargeability. Cycling capacity retention rate at 100^th cycle （$10o） gradually increased from 77.3% （x= 0.90） to 84.6% （x= 1.10）, which resulted from the increase in Ni content and the c/a ratio of the LaNi5 phase with x value increasing.

Microstructure and electrochemical characteristics of La_(0.7)Ce_(0.3)Ni_(3.75)Mn_(0.35)Al_(0.15)Cu_(0.75-x)(V_(0.81)Fe_(0.19))_x hydrogen storage alloys

Microstructure and electrochemical characteristics of La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-x（V0.81Fe0.19）x hydrogen storage alloys were investigated. XRD indicated that La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-x（V0.81Fe0.19）x alloys consisted of a single phase with CaCus-type structure, and the lattice parameter a and cell volume V increased with increasing x value. The maximum discharge capacity first increased from 319.0 （x=0） to 324.0 mAh/g （x=0.05）, and then decreased to 307.0 mAh/g （x=0.20）. The high-rate dischargeability at the discharge current density of 1200 mA/g first increased from 52.1% （x=0） to 59.1% （x=0.15）, and then decreased to 55.4% （x=0.20）. The hydrogen diffusion in the bulky alloy was responsible for the high-rate dischargeability. Cycling stability first increased with increasing x from 0 to 0.10 and then de- creased when x increased to 0.20, which was resulted fi＇om the synthesized effect of the improvement of the pulverization resistance and the decrease of corrosion resistance.