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.

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.

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.

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.

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.

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.

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.

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.

High-temperature electrochemical performance and phase composition of Ti_(0.7) Zr_(0.5) V_(0.2) Mn_(1.8-x)Ni_x hydrogen storage electrode alloys

The rapid development of electric vehicles demands the development of high performance nickel metal hydride battery that is able to endure high temperature. The discharge properties of Ti 0.7 Zr 0.5 V 0.2 Mn 1.8- x Ni x ( x =0.4, 0.8, 1.1, 1.4, 1.7)hydrogen storage alloys was investigated and its phase composition was analyzed using X ray diffraction. The results show that the cycling life was improved as the content of nickel increases. When x =0.4, 0.8, 1.1 and 1.4, the main phase is MgZn 2 type C14 Laves phase and the second one is cubic TiNi phase. When x =1.7, the Laves phase structure disappears. EDAS analysis shows that the increase of nickel content is effective in suppressing the dissolution of vanadium component in alloys. [

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.

Electrodeposited Cobalt-Iron Alloy Thin-Film for Potentiometric Hydrogen Phosphate-Ion Sensor

A cobalt-iron alloy thin-film electrode-based electrochemical hydrogen-phosphate-ion sensor was prepared by electrodepositing on an Au-coated Al2O3 substrate from an aqueous solution of metal-salts. The use of a cobalt-iron alloy electrode greatly improved the hydrogen-ion sensor response performance, i.e., the sensor worked stably for more than 7 weeks and showed a quick response time of several seconds. Among the cobalt and iron alloy systems tested, the electrodeposited Co58Fe42 thin-film electrode showed the best EMF response characteristics, i.e., the sensor exhibited a linear potentiometric response to hydrogen-phosphate ion at the concentration range between 1.0 × 10–5 and 1.0 × 10–2 M with the slope of –43 mV/decade at pH 5.0 and at 30℃. A sensing mechanism of the Co-based potentiometric hydrogen-phosphate ion sensor was proposed on the basis of results of instrumental analysis.

Effects of sputtering conditions on electrochemical behavior and physical properties of Ni-Mo alloy electrode

Sputtering method was used to prepare Ni-Mo alloy electrodes for hydrogen production in alkaline solution. The influences of the working pressure during deposition and the substrate temperature on the electrochemical behavior of electrode were characterized by steady-state polarization plot and Tafel polarization curve measurements. And the physical properties of electrodes were characterized by XRD, SEM, AFM and EDS. It is found that the overpotential is significantly influenced by the working pressure which affects critically the electrode surface morphology, and two Tafel regions are observed for each sample. The overpotential value does not change very much with the substrate temperature. The XRD results indicates that the electrodes should be considered nanocrystalline. Thornton model for the microstructure of sputter-deposited electrodes is referred to explain the observed microstructure change.

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.

Structure and electrochemical hydrogen storage characteristics of La_(0.8-x)Pr_xMg_(0.2)Ni_(3.15)Co_(0.2)Al_(0.1)Si_(0.05) (x=0-0.4) electrode alloys

For the purpose of improving the electrochemical cycle stability of the La-Mg-Ni based A2B7-type electrode alloys, both reducing Mg content and substituting La with Pr were adopted. The La0.8-xPrxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4) electrode alloys were fabricated by casting and annealing. The investigation on the structures and electrochemical performances of the alloys was performed. The obtained results reveal that the as-cast and annealed alloys comprise two major phases, (La,Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu 5-type structure, as well as a little residual LaNi3 phase. It is also found that the addition of Pr element observably affects the electrochemical hydrogen storage characteristics of the alloys, just as the discharge capacity and high rate discharge ability (HRD) first rise then fall with the growing of Pr content, and among all the alloys, the as-cast and annealed (x=0.3) alloys generate the largest discharge capacities of 360.8 and 386.5 mA·h/g, respectively. Additionally, the electrochemical cycle stability of all the alloys markedly grows with the increase of Pr content. The capacity retaining rate (S100 ) at the 100th charging and discharging cycle is enhanced from 64.98% to 77.55% for the as-cast alloy, and from 76.60% to 95.72% for the as-annealed alloy by rising Pr content from 0 to 0.4. Furthermore, the substitution of Pr for La results in first increase and then decrease in the hydrogen diffusion coefficient (D), the limiting current density (IL ) as well as the electrochemical impedance.

Effects of rapid quenching on structure and electrochemical characteristics of La_(0.5)Ce_(0.2)Mg_(0.3)Co_(0.4)Ni_(2.6-x)Mn_x(x=0-0.4) electrode alloys

The La-Mg-Ni system PuNi3-type La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx(x=0,0.1,0.2,0.3,0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the rapid quenching on the structure and electrochemical characteristics of the alloys were studied. The results obtained by XRD,SEM and TEM indicate that the as-cast and quenched alloys mainly consist of two major phases,(La,Mg)Ni3 and LaNi5,as well as a residual phase LaNi. The rapid quenching does not exert an obvious influence on the phase composition of the alloys,but it leads to an increase of the LaNi5 phase and a decrease of the(La,Mg)Ni3 phase. The as-quenched alloys have a nano-crystalline structure,and the grain sizes of the alloys are in the range of 20-30 nm. The results by the electrochemical measurements indicate that both the discharge capacity and the high rate discharge(HRD) ability of the alloy first increase and then decrease with the variety of quenching rate and obtain the maximum values at the special quenching rate which is changeable with the variety of Mn content. The rapid quenching significantly improves the cycle stabilities of the alloys,but it slightly impairs the activation capabilities of the alloys.

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.

Electrode Process of Y^(3+) Ion on Copper Electrode and Surface Alloying

The reduction of yttrium ion on copper electrode in NaCl-KCl-YCl3 molten salts has been investigated.The results indicate that several humps for formation of intermetallic compounds occur before metallic yttrium is produced. The formation of intermetallic compounds is controlled by diffusion of yttrium into copper electrode. The application of theoretical results to diffusion of yttrium atoms into copper substrate is discussed also.

ELECTRODE PERFORMANCES OF MELT-SPINNED AB_2 TYPE Zr-BASED HYDROGEN STORAGE ALLOYS

１ＩＮＴＲＯＤＵＣＴＩＯＮＩｔｉｓａｓｕｍｅｄｔｈａｔｔｈｅｅｌｅｃｔｒｏｃｈｅｍｉｃａｌｐｒｏｐｅｒｔｉｅｓｄｅｐｅｎｄｏｎｂｏｔｈｔｈｅｃｈｅｍｉｃａｌｃｏｍｐｏｓｉｔｉｏｎａｎｄｔｈｅｍｉｃｒｏｓｔｒｕｃｔｕｒｅｏｆｈｙｄｒｏｇｅｎｓｔｏｒａ...