Influence of rapid quenching on cyclic stability of La-Mg-Ni system (AB_3-type) electrode alloys

Aiming at the improvement of the cyclic stability of La-Mg-Ni system （PuNi3-type） hydrogen storage alloy, Ni in the alloy was partly substituted by Fe. The electrode alloys of La0.7Mg0.3Co0.45Ni255-xFex （x=0, 0.1, 0.2, 0.3, 0.4） were prepared by casting and rapid quenching. The influence of the quenching on cyclic stability as well as structure of the alloys was investigated in detail. The results of electrochemical measurement indicated that rapid quenching significantly improved cyclic stability. When the quenching rate rose from 0 （As-cast was defined as a quenching rate of 0 m/s） to 30 m/s, the cyclic life of Fe-free alloy （x=-0） increased from 81 to 105 cycles, and for alloy containing Fe（x=0.4）, it grew from 106 to 166 cycles at a current density of 600 mA/g. The results obtained by XRD, TEM and SEM revealed that the as-cast and quenched alloys had multiphase structures, including two major phases （La, Mg）Ni3 and LaNi5 as well as an imptLrity phase LaNi2. Rapid quenching helped the formation of an amorphous-like structure in Fe containing alloys.

Effects of substituting Ni with M (M=Cu, Al and Mn) on microstructures and electrochemical characteristics of La-Mg-Ni system (PuNi_3-type) electrode alloys

In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Cu, Al, Mn; x=0, 0.1) were prepared by casting and rapid quenching. The effects of element substitution and rapid quenching on the microstructures and electrochemical performances of the alloys were investigated. The results by XRD, SEM and TEM show that the alloys have a multiphase structure, including the (La, Mg)Ni3 phase, the LaNi5 phase and the LaNi2 phase. The rapid quenching and element substitution have an imperceptible influence on the phase compositions of the alloys, but both change the phase abundance of the alloys. The rapid quenching significantly improves the composition homogeneity of the alloys and markedly decreases the grain size of the alloys. The Cu substitution promotes the formation of an amorphous phase in the as-quenched alloy, and a reversal result by the Al substitution. The electrochemical measurement indicates that the element substitution decreases the discharge capacity of the alloys, whereas it obviously improves the cycle stability of the alloys. The positive influence of element substitution on the cycle life of the alloys is in sequence Al>Cu>Mn, and negative influence on the discharge capacity is in sequence Al>Mn>Cu. The rapid quenching significantly enhances the cycle stability of the alloys, but it leads to a different extent decrease of the discharge capacity of the alloys.

Effects of Ca substitution and surface treatment on electrochemical performances of Ml_(1.0-x) Ca_xNi_(4.0) Co_(0.6) Al_(0.4) hydrogen storage alloy electrodes

The influences of Ca substitution for Ml and surface treatment on electrochemical performances of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 hydrogen storage alloy electrode were investigated. Ca substitution with x <0.2 for Ml could improve its discharge capacity, but Ca substitution with x >0.2 could decrease the capacity. It was also found that Ca substitution deteriorates the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode. In order to improve these properties of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 alloy electrode, the alloy was treated in 6 mol/L KOH+0.02 mol/L KBH 4 solution. The results showed that the surface treatment improves the electrochemical performances such as the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode. :The influences of Ca substitution for Ml and surface treatment on electrochemical performances of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 hydrogen storage alloy electrode were investigated. Ca substitution with x <0.2 for Ml could improve its discharge capacity, but Ca substitution with x >0.2 could decrease the capacity. It was also found that Ca substitution deteriorates the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode. In order to improve these properties of Ml 1.0- x Ca x Ni 4.0 Co 0.6 Al 0.4 alloy electrode, the alloy was treated in 6 mol/L KOH+0.02 mol/L KBH 4 solution. The results showed that the surface treatment improves the electrochemical performances such as the electrocatalytic activity, high rate dischargeability and cycling durability of the alloy electrode.

Effect of deep cryogenic treatment on mechanical behavior of a Cu-Cr-Zr alloy for electrodes of spot welding

The effects of deep cryogenic treatment on mechanical behavior of a Cu-Cr-Zr alloy for electrodes of spot welding were investigated employing Brinell-hardness testing unit, abrasion examination machine, electronic almighty testing machine and X-ray stress analyzer. Tensile fracture surfaces of the alloy were characterized by scanning electronic microscope （SEM） with energy dispersive X-ray spectroscopy （EDS）. The results showed that, after deep cryogenic treatment, σb and σ0.2 increased 23 MPa and 21 MPa respectively, the wear rate of the alloy exhibited the trend of decrease with the decreasing temperature and increasing time of deep cryogenic treatment, and the surface residual stress of the alloy was partially eliminated by deep cryogenic treatment.

Electrochemical Hydrogen Storage Performances of the Si Added La-Mg-Ni-based A_2B_7-type Electrode Alloys for Ni/MH Battery Application

The casting and annealing technologies were applied to fabricate the La0.8Mg0.2Ni3.3Co0.2Six （x = 0-0.2） electrode alloys. The effects of Si content and annealing temperature on the structure and electrochemical performances of the alloys were investigated systematically. The analyses of XRD and SEM show that all the alloys possess a multiphase structure, involving two main phases （La, Mg）2Ni7 and LaNi5 as well as a residual phase LaNi3. The addition of Si brings on an evident increase in the LaNi5 phase and a decrease in the （La, Mg）2Ni7 phase, without altering the main phase component of the alloy, which also makes the lattice constants and cell volumes of the alloy enlarged. Likewise, the annealing treatment engenders the same action on the lattice constants and cell volumes as adding Si. Simultaneously, it gives rise to the variation of the phase abundance and the coarsening of the alloy grains. The electrochemical measurements indicate that the addition of Si ameliorates the cycle stability of the as-cast and annealed alloys significantly, but impairs their discharge capacities clearly. Similarly, the annealing treatment makes a positive contribution to the cycle stability of the alloy evidently, and the discharge capacity of the alloy shows a maximum value with annealing temperature rising. Furthermore, the high rate discharge ability （HR） first augments and then declines with the rising of Si content and annealing temperature.

Effect of cobalt content on electrochemical performance of La-Mg-Ni system (Ce_2Ni_7-type) electrode alloys

In order to improve the cyclic stability of La-Mg-Ni system （Ce2Ni7-type） alloy electrode, small amount of Co was added in La0.75Mg0.25Ni3.5 alloy. The effect of Co on electrochemical performance and microstructure of the alloys were investigated in detail. XRD results showed that the alloys had multiphase structure composed of （La, Mg）2Ni7, LaNi5 and small amount of LaNi2 phases. The discharge capacity of the alloys first increased and then decreased with increasing Co content. At a discharge current density of 900 mA/g, the HRD of the alloy electrodes increased from 81.3% （x=0） to 89.2 % （x=0.2）, and then reduced to 87.8 % （x=0.6）. After 60 charge/discharge cycles, the capacity retention rate of the alloys enhanced from 52.67% to 61.32%, and the capacity decay rate of the alloys decreased from 2.60 to 2.05 mAh/g per cycle with increasing Co content. The obtained results by XPS and XRD showed that the fundamental reasons for the capacity decay of the La-Mg-Ni system （Ce2Ni7-type） alloy electrodes were corrosion and oxidation as well as passivation of Mg and Lain alkaline solution.

Tunable surface plasmon-polariton resonance in organic light-emitting devices based on corrugated alloy electrodes

We report a feasible method to realize tun able surface plasm on-polarit on(SPP)res onance in orga nic light-emitt ing devices(OLEDs)by emplo ying corrugated Ag-Al alloy electrodes.The excited SPP res onance in duced by the periodic corrugations can be precisely tuned based on the composition ratios of the Ag-Al alloy electrodes.With an appropriate composition ratio of the corrugated alloy electrode,the photons trapped in SPP modes are recovered and extracted effectively.The 25%in creaseme nt in luminance and 21%enhan ceme nt in curre nt efficie ncy have bee n achieved by using the corrugated Ag-Al alloy electrodes in OLEDs.

An investigation on electrochemical performances of as-cast and annealed La_(0.8)Mg_(0.2)Ni_(3.3)Co_(0.2)Si_x(x=0-0.2)alloy electrodes for Ni/MH battery application

The La–Mg–Ni-based A2B7-type La0.8Mg0.2Ni3.3Co0.2Six(x=0-0.2)electrode alloys were prepared by casting and annealing.The influences of the additional silicon and the annealing treatment on the structure and electrochemical performances of the alloys were investigated systemically.Both of the analyses of XRD and SEM reveal that the as-cast and annealed alloys are of a multiphase structure,involving two main phases(La,Mg)2Ni7 and LaNi5 as well as one minor phase LaNi3.The addition of Si and annealing treatment bring on an evident change in the phase abundances and cell parameters of(La,Mg)2Ni7 and LaNi5 phase for the alloy without altering its phase structure.The phase abundances decrease from 74.3%(x=0)to 57.8%(x=0.2)for the(La,Mg)2Ni7 phase,and those of LaNi5 phase increase from 20.2%(x=0)to 37.3%(x=0.2).As for the electrochemical measurements,adding Si and performing annealing treatment have engendered obvious impacts.The cycle stability of the alloys is improved dramatically,being enhanced from 80.3% to 93.7% for the as-annealed(950 °C)alloys with Si content increasing from 0 to 0.2.However,the discharge capacity is reduced by adding Si,from 399.4 to 345.3 mA·h/g as the Si content increases from 0 to 0.2.Furthermore,such addition makes the electrochemical kinetic properties of the alloy electrodes first increase and then decrease.Also,it is found that the overall electrochemical properties of the alloys first augment and then fall with the annealing temperature rising.

Well-aligned Ni Pt alloy counter electrodes for high-efficiency dye-sensitized solar cell applications

Development of cost-effective and robust counter electrodes(CEs) is a persistent objective for highefficiency dye-sensitized solar cells(DSSCs). To achieve this goal, we present here the hydrothermal synthesis of well-aligned Ni Pt alloy CEs, which is templated by ZnO nanowires and nanosheets. The preliminary results demonstrate that Ni Pt alloy electrodes are featured by increased charge-transfer processes and electrocatalytic activity in comparison with expensive Pt CE, yielding power conversion efficiencies of 8.29% and 7.41% in corresponding DSSCs with Ni Pt nanowire and nanosheet alloy CEs, respectively. Additionally, the Ni Pt alloy CEs also display extraordinary dissolution-resistant ability when suffering longterm utilization in liquid-junction DSSCs.

Characteristics of multi-component Ml-based hydrogen storage alloys and their hydride electrodes

A series of multi-component M1-based hydrogen storage alloys witha cobalt atomic ratio of 0.40-0.75 were prepared. The electrochemicalproperties under different charge-discharge conditions and PCTcharaceristics measured by electrochemical method were investigated.The addition of other alloying elements for partial substitution ofCo low- ers the hydrogen equilibrium pressure and discharge capacity,but improves the cycling stability and makes the alloys keep nearlythe same rate discharge capability and high-temperature dischargecapability as those of the compared alloy. The reasons werediscussed.

Electocbemical Process of Ti-Ni Alloy Electrodes by Cyclic Voltammetry

The electrochemical process of Ti-Ni alloy electrode was studied by using cyclic voltammetry. The hydrogen-absorbing electrode could be approximately regarded as a reversible hydrogen elecrede. The con- trolling steps of the discharging process varying with the anodic overpotentials were investigated and the effect ofelecrode constituent modification or Zr adulteation on the electrochemical behavior was also studied.

Surface Modification of AB_2 and AB_5 Hydrogen Storage Alloy Electrodes by the Hot-Charging Treatment

The effect of the hot-charging treatment on the performance of AB(2) and AB(5) hydrogen storage alloy electrodes was investigated. The result showed that the treatment can markedly improve the voltage plateau ratio (VPR), the high rate discharge ability (HRDA), the diffusion coefficient of hydrogen DH and the discharge capacity of the AB2 hydrogen storage alloy electrode. The SEM analysis showed that the hot-charging treatment brings about a Ni-rich surface due to the dissolution of Zr oxides. It is also very helpful for the improvement of the kinetic properties of AB2 hydrogen storage alloy electrode because the microcracking of the surface results in fresh surface. This can be the basic modification treatment for NiMH battery used in electric vehicles (EVs) in the future. But for AB(5) type alloys, the treatment has the disadvantage of impairing the comprehensive electrochemical properties, because the surface of the alloy may be corroded during the treatment. The mechanism of the surface modification of the electrode is also proposed.

Study on hydrogen evolution performance of the carbon supported PtRu alloy film electrodes

The carbon supported PtRu alloy film electrodes having Pt about 0.10 mg/cm2 or even less were prepared by ion beam sputtering method （IBSM）. It was valued on the hydrogen analyse performance, the temperature influence factor and the stability by electroanalysis hydrogen analyse method. It was found that the carbon supported PtRu alloy film electrodes had higher hydrogen evolution performance and stability, such as the hydrogen evolution exchange current density （j0） was increase as the temperature （T） rised, and it overrun 150 mA/cm2 as the trough voltage in about 0.68V, and it only had about 2.8% decline in 500 h electrolytic process. The results demonstrated that the carbon supported PtRu alloy film electrodes kept highly catalytic activity and stability, and it were successfully used in pilot plant for producing H2 on electrolysis of H2S.

First-principles calculations and experimental studies of Sn-Zn alloys as negative electrode materials for lithium-ion batteries

The physical characters and electrochemical properties of various phases in a Sn-Zn electrode, such as formation energy, plateau potential, specific capacity, as well as volume expansion, were calculated by the first-principles plane-wave pseudo-potential method based on the den- sity functional theory. Sn-Zn films were also deposited on copper foils by an electroless plating technique. The actual composition and chemical characters were explored by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, plasma atomic emission spectrometry （ICP）, and constant current charge/discharge measurements （CC）. The results show that separation phases with tin and zinc including a small quantity of Cu6Sn5 phase were obtained, the initial lithium insertion capacity of the Sn-Zn film was 661 mAh/g, and obvious potential pla- teaus of about 0.4 V and 0.7 V were displayed, which is in accordance with the results of theoretical calculations. The capacity of the Sn-Zn film decreased seriously with the increase of cycle number.

Effect of annealing temperature on microstructure and electrochemical performance of La_(0.75)Mg_(0.25)Ni_(3.5)Co_(0.2) 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.

Structures and electrochemical performances of La_(0.75-x)Zr_xMg_(0.25)Ni_(3.2)Co_(0.2)Al_(0.1) (x=0-0.2) electrode alloys prepared by melt spinning

The La-Mg-Ni system A2B7-type electrode alloys with nominal composition La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1(x=0,0.05, 0.1,0.15,0.2)were prepared by casting and melt-spinning.The influences of melt spinning on the electrochemical performances as well as the structures of the alloys were investigated.The results obtained by XRD,SEM and TEM show that the as-cast and spun alloys have a multiphase structure,consisting of two main phases(La,Mg)Ni3 and LaNi5 as well as a residual phase LaNi2.The melt spinning leads to an obvious increase of the LaNi5 phase and a decrease of the(La,Mg)Ni3 phase in the alloys.The results of the electrochemical measurement indicate that the discharge capacity of the alloys(x≤0.1)first increases and then decreases with the increase of spinning rate,whereas for x>0.1,the discharge capacity of the alloys monotonously falls.The melt spinning slightly impairs the activation capability of the alloys,but it significantly enhances the cycle stability of the alloys.

Cycle Stabilities of La_(0.7)Mg_(0.3)Ni_(2.55-x)Co_(0.45)M_x (M=Fe, Cu, Al;x=0, 0.1) Electrode Alloys Prepared by Casting and Rapid Quenching

La-Mg-Ni system (PuNi3-type) hydrogen storage alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Fe, Cu, Al; x=0, 0.1) were prepared by casting and rapid quenching. Aiming to improve the cycle stabilities of the alloys, Ni in the alloy was partly substituted by Fe, Cu and Al. The effects of the substitution of Fe, Cu and Al for Ni and the rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that the element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Cu obviously increases the amount of the LaNi2 phase. The substitution of Al and Fe leads to a great refinement of the as-quenched alloy′s grains. The substitution of Al strongly restrains the formation of the amorphous in the as-quenched alloy, but the substitution of Fe and Cu is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Cu and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive impact of the substitution elements on the cycle stabilities of the as-cast alloys is ranked in proper order Al>Fe>Cu, and for as-quenched alloys, the order is Fe>Al>Cu. Rapid quenching engenders an unconscious influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.

Effect of Cerium on Microstructure and Electrochemical Performance of Ti-V-Cr-Ni Electrode Alloy

Effect of cerium on the microstructure and electrochemical performance of the Ti0.25V0.35-xCexCr0.1Ni0.3（x=0,0.005）electrode alloy was investigated by X-ray diffraction（XRD）,field emission scanning electron microscopy/energy dispersive X-ray spectrometry（FESEM-EDS）,and electrochemical impedance spectroscopy（EIS）measurements.On the basis of XRD and FESEM-EDS analysis,the alloy was mainly composed of V-based solid solution with body-centered-cubic structure and TiNi-based secondary phase.Ce did not exist in two phases,instead,it existed as Ce-rich small white particles,with irregular edges,distributed near the grain boundaries of the V-based solid solution phase.Discharge capacity,cycle stability,and high-rate discharge ability of the alloy electrode were effectively improved with the addition of Ce at 293 K.It was very surprising that the charge retention was abnormal with larger discharge capacity after standing at the open circuit for 24 h.EIS indicated that addition of Ce improved the dynamic performance,which caused the charge transfer resistance（RT）to decrease and exchange current density（I0）to increase markedly.The exchange current density of the electrochemical reaction on the alloy surface with Ce addition was about 2.07 and 3.10 times larger than that of the alloy without Ce at 303 and 343 K,respectively.The diffusion coefficient of hydrogen（D）in the bulk alloy electrode decreased with addition of Ce,but it did not decrease so much,and the apparent activation energy（△rH）was far higher than that of the AB5 type alloy.

Electrochemical behavior and underpotential deposition of Sm on reactive electrodes(Al,Ni,Cu and Zn)in a LiCl-KCl melt

Sm extraction from a LiCl-KCl melt was carried out by forming alloys on various electrodes,including Al,Ni,Cu,and liquid Zn,and the electrochemical behaviors of the resultant metal products were investigated using different electrochemical techniques.While Sm metal deposition via the conventional two-step reaction process was not noted on the inert electrode,underpotential deposition was observed on the reactive electrodes because of the latter's depolarization effect.The depolarization effects of the reactive electrodes on Sm showed the order Zn>Al>Ni>Cu.Sm-M(M=Al,Ni,Cu,Zn)alloys were deposited by galvanostatic and potentiostatic electrolysis.The products were fully characterized by X-ray diffractometry(XRD)and scanning electron microscopy(SEM)-energy dispersive spectrometry(EDS),and the stability of the obtained M-rich compounds was determined.Finally,the relationship between the electrode potential and type of Sm-M intermetallic compounds formed was assessed on the basis of the observed electrochemical properties and electrodeposits.

Influence of Annealing Treatment on Microstructure and Cycling Stability of La-Rich Ml(NiCoMnAl)_5 Alloy Electrode for Ni/MH Batteries

The crystallographic structure, microstructure, composition homogeneity and electrode charge-discharge cycling stability were investigated of the as-cast and annealed La-rich mischmetal (designating Ml)-based hydrogen storage alloy with a composition of MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3). X-ray diffraction analysis shows that the MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) alloy is composed of the dominant phase with a CaCu_5-type hexagonal structure and small amounts of the second phase with a La_2Ni_7-type structure. The annealing heat treatment conducted at 1273 K for 10 h results in decrease of the crystal lattice strain and composition segregation, disappearance of the dendrite structure and growth of the crystal grain of the MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) alloy. The annealing causes the cycle life to be increased by about 30% over the as-cast alloy electrode. The cycling stability of the alloy electrode is improved significantly upon annealing. The cause of the improvement in the cycling stability was discussed based on the alloy composition distribution and microstructure changes due to annealing.