Effect of Some Metal Ion Dopants on Electrochemical Properties of Ni(OH)_2 Film Electrode

The Ni(OH) 2 film electrodes doped respectively with alkali-earth metal aluminum, lead, partial transition metal and some rare-earth metal(altogether 17 kinds of metals) ions were prepared by cathode electrodeposition. The electrode reaction reversibility, the difficult extent of oxygen evolution, the proton diffusion coefficient, the discharge potential of middle value and the active material utilization of the Ni(OH) 2 film electrode were compared with those of the ones doped with the metal ions by means of cyclic voltammetry, potential step and constant current charge-discharge experiments. It was found that Ca 2+ , Co 2+ , Cd 2+ , Al 3+ etc. have obviously positive effect.

MICROSTRUCTURE AND ELECTROCHEMICAL CHARACTERISTICS OF Zr_(0.9)Ti_(0.1)(Ni_(1.1)Mn_(0.7)V_(0.2))_x METAL HYDRIDE ELECTRODE

The crystal structure, the phase composition and the electrochemical characteristics of Zr0.9Ti0.1(Ni1.1Mn0.7V0.2)x (x=0.90, 0.95, 1.00, 1.05) alloys were investigated by means of XRD, SEM, EDS and electrochemical measurements. It was shown that all alloys are multiphase with C15 Laves phase as a main phase along with C14 phase and some secondary phases. And the amounts of the C14 phase and secondary phases in the four alloys increases with decreasing x. The results indicated that the various stoichiometric ratios have great effects on the electrochemical characteristics such as the maximum discharge capacity, discharge rate capability and self-discharge properties etc. for Zr0.9Ti0.1(Ni1.1Mn0.7 V0.2)X (x=0.90, 0.95, 1.00, 1.05) alloys. The hyper-stoichiometric Zr0.9 Ti0.1(N1.1Mn0.7 V0.20)1.05 exhibits the maximum discharge capacity of 332mAh-g-1. The C14 phase and secondary phases seems to improve discharge rate capability of the alloys.

Electrochemical Properties and Crystal Structure of Rare Earth AB_(3.5)-Type Alloy as Negative Electrode Material in MH-Ni Battery

The electrochemical characteristics and crystal structure of metal hydride electrode of AB_(3.5)-type alloy was studied. The electrochemical properties of the metal hydride electrode were investigated at room temperature and -30 ℃. The partial substitution of Ni by Al element causes an expansion of the lattice cell and increases the specific capacity and rate discharge ability of the alloy.

Effects of annealing on microstructures and electrochemical properties of La_(0.8)Mg_(0.2)Ni_(2.4)Mn_(0.10)Co_(0.55)Al_(0.10) alloy

The La0.8Mg0.2Ni2.4Mn0.10Co0.55Al0.10 alloy was prepared by induction melting. The structural and morphological characterizations were performed by means of X-ray powder diffraction （XRD） and scanning electron microscopy （SEM）. The electrochemical measurements were performed using LAND and CH/660b electrochemical workstation. The main phases of the alloy were LaNi5 and （La,Mg）Ni3. After annealing, the maximum discharge capacity, cycle stability and high rate dischargeability （HRD） were improved obviously. The maximum discharge capacity reached 373.80 mAh/g （T=1173 K）, the C100/Cmax（%） was 72.63% （T=1173 K）, and the value of HRD reached 51.8% at a discharge current density of 1150 mA/g （T=1173 K）. The cyclic voltammetry （CV） and potentiodynamic polarization were also studied.

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.

Effects of Annealing Temperature on Microstructure and Electrochemical Properties of Perovskite-type Oxide LaFeO3 as Negative Electrode for Metal Hydride/Nickel（MH/Ni） Batteries

We reported the effects of annealing temperatures on microstructure and electrochemical properties of perovskite-type oxide LaFeO3 prepared by stearic acid combustion method. X-Ray diffraction（XRD） patterns show that the annealed LaFeO3 powder has orthorhombic structure. Scanning electron microscopy（SEM） and transmission electron microscopy（TEM） images show the presence of homogeneously dispersed, less aggregated, and small crystals（30--40 nm） at annealing temperatures of 500 and 600 ℃. However, as the annealing temperature was increased to 700 and 800 ℃, the crystals began to combine with each other and grew into further larger crystals（90--100 nm）. The electrochemical performance of the annealed oxides was measured at 60 ℃ using chronopotentiometry, potentiodynamic polarization, and cyclic voltammetry. As the annealing temperature increased, the discharge capacity and anti-corrosion ability of the oxide electrode first increased and then decreased, reaching the optimum values at 600 ℃, with a maximum discharge capacity of 563 mA-h/g. The better electrochemical performance of LaFeO3 annealed at 600℃ could be ascribed to their smaller and more homogeneous crysals.

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.

Zr-Cr-Ni BASED MULTICOMPONENT METAL HYDRIDE ELECTRODES

ＺｒＣｒＮｉＢＡＳＥＤＭＵＬＴＩＣＯＭＰＯＮＥＮＴＭＥＴＡＬＨＹＤＲＩＤＥＥＬＥＣＴＲＯＤＥＳ①ＹａｎｇＸｉａｏｇｕａｎｇ，ＬｅｉＹｏｎｇｑｕａｎ，ＣｈｅｎＹａｎｇｌｉｎ，ＷａｎｇＱｉｄｏｎｇＤｅｐａｒｔｍｅｎｔｏｆＭａｔｅｒｉａｌｓＳｃｉｅｎｃ...

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.

IMPROVEMENT IN ELECTROCHEMICAL PERFORMANCES OF Mm(NiCoMnAl)_5 ELECTRODES BY SURFACE MODIFICATION

ＩＭＰＲＯＶＥＭＥＮＴＩＮＥＬＥＣＴＲＯＣＨＥＭＩＣＡＬＰＥＲＦＯＲＭＡＮＣＥＳＯＦＭｍ（ＮｉＣｏＭｎＡｌ）５ＥＬＥＣＴＲＯＤＥＳＢＹＳＵＲＦＡＣＥＭＯＤＩＦＩＣＡＴＩＯＮ①ＣｈｅｎＷｅｉｘｉａｎｇＤｅｐａｒｔｍｅｎｔｏｆＭａｔｅｒｉａｌｓＳｃｉｅｎ...

Electrode properties and phase composition of Ti_(0.5)Ni_(0.25)Al_(0.25) hydrogen storage alloys and theoretical simulation

Ti0.5Al0.25Ni0.25 alloy prepared by vacuum induction melting was studied.The phase composition was analyzed with X-ray technique and EDS analysis,and its electrochemical properties were investigated at various temperatures.Electrochemical reaction kinetic parameters were also studied with proper electrochemical techniques.The influence of the secondary corrosion reaction on the anodic linear polarization measurement was also analyzed by theoretical simulation.The results show that,proper ball-milling with nickel powders is beneficial to electrochemical performance.The theoretical simulation proves that,the existence of the side reaction can disturb the measurement of electrochemical reaction kinetic parameters.

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.

煅烧对空气电极的多孔结构和电化学性能的影响

优化空气电极的孔道结构对提升电极的电化学性能至关重要。通过电极多孔结构的重组,可以提高氧气的传输速率,从而实现金属空气电池的高能量密度和长放电寿命。采用扫描电镜、差热分析仪、比表面积测试仪、润湿角测试仪和电化学测试仪等检测技术,研究了不同煅烧温度(200、250、300、350、400℃)对空气电极的表观形貌、微孔结构和电化学性能的影响,并进一步测试了镁基空气电池的放电性能。结果表明,随着煅烧温度升高,电极中黏结剂聚四氟乙烯(PTFE)的纤维熔融状态改变了其微孔结构分布(包括气孔和液孔),从而影响了电极的氧还原电化学性能和放电寿命。尤其在接近PTFE相变点(343℃)的煅烧温度350℃下制备的空气电极,具有均匀的孔径分布和最佳疏水特性(包含疏水点和气体扩散孔道)。因此,空气电极表现出最小电极极化(-0.45 V极化电位下,电极电流密度为159.1 mA/cm^(2))、最长放电寿命(15 mA/cm^(2)电流密度下,放电时长为39.0 h),较大的容量及功率密度(分别为37.4 A·h和13.05 mW/cm^(2))。

Crystallographic and electrochemical characteristics of melt-spun Ti-Zr-Ni-Cu alloys

Ti44Zr32Ni22Cu2 and Ti41Zr29Ni28Cu2 alloys were prepared by the melt-spinning method. The phase structure was analyzed by X-ray diffraction,and the electrochemical performances of the melt-spun alloys were investigated. The results indicated that the Ti44Zr32Ni22Cu2 alloy was composed of the icosahedral quasicrystals and amorphous phases,and the Ti41Zr29Ni28Cu2 alloy comprised icosahedral quasicrystals,amorphous,and Laves phases. The maximum discharge capacity was 141 mAh/g for the Ti44Zr32Ni22Cu2 alloy and 181 mAh/g for the Ti41Zr29Ni28Cu2 alloy,respectively. The Ti41Zr29Ni28Cu2 alloy also showed a better high-rate dischargeability and cycling stability. The better electrochemical properties should be ascribed to the high content of Ni,which was beneficial to the electrochemical kinetic properties and made the alloy more resistant to oxidation,as well as to the Laves phase in the Ti41Zr29Ni28Cu2 alloy,which could work as the electro-catalyst and the micro-current collector.

Influence of Doped Elements on Electrochemical High Temperature Performance of La-riched Hydrogen Storage Material

The effects of small amounts of added elements such as aluminum, titanium and zirconium to MlNi 3.8(CoMn) 1.2 on its electrochemical performances and performances at high temperatures were investigated.It is found that the addition of aluminum brings about a significant increase in the discharge capacity at high temperatures,and the capacity decay during repeated charge-discharge cycles and the self-discharge are both suppressed, while the rate capability decreases.The alloy containing zirconium exhibits a longer cycle life and a better rate capability,but a much lower discharge capacity.The addition of titanium improves the rate capability, but the capacity decreases greatly.An X-ray diffraction analysis indicates that a second phase exists in the alloy with additive Zr or Ti,which improves the discharge-rate characteristics,and the superior stability of the alloy with additive Al may be due to the expansion of lattice parameters and cell volume.

先进镍氢电池负极材料的研究进展

Ni/MH二次电池由于具有安全性和优异的综合性能等优势而被广泛用于日常生活和航空航天等领域,其中负极材料的迭代推动了镍氢电池的发展。本文详细综述了目前在市场需求推动下负极材料的研究进展,解释了涉及金属氢化物的电化学反应基本原理,重点介绍了常温、高温和低温环境下AB5合金以及高容量超晶格AB_(3)、A_(2)B_(7)、A_(5)B_(19)和AB_(4)合金的研究进展和相转变机制,最后,在新能源大力发展的背景下,讨论了镍氢电池及负极材料面临的挑战和机遇。

Structure and electrochemical characteristics of LaNi_5-Ti_(0.10)Zr_(0.16)V_(0.34)Cr_(0.10)Ni_(0.30) composite alloy electrode

Composite LaNi5+x wt.% Ti0.10Zr0.16V0.34Cr0.10Ni0.30 (x=0, 1, 5, 10) alloys were prepared by two-step re-melting. X-ray diffractometer (XRD), scanning electron microscopy (FESEM), energy dispersive spectrometry (EDS), inductively coupled plasma (ICP) and electrochemical impedance spectroscopy (EIS) analyses showed that the matrix phase of LaNi5 alloy with CaCu5 structure remained unchanged after additive alloy was added, the amount of the second phase increased with increasing x. The synergetic effect withi...

稀土成分对贮氢合金RE（NiCoMnTi）_5电化学性能的影响

系统地研究了稀土组元（ＲＥ＝Ｌａ１－ｘ－ｙ－ｚＣｅｘＮｄｙＰｒｚ）对贮氢合金ＲＥ（ＮｉＣｏＭｎＴｉ）５电化学性能的影响．结果表明，Ｌａ，Ｃｅ，Ｎｄ和Ｐｒ的含量及比例对合金性能有显著影响．为描述稀土组元综合效应，本文引入四组元受约束的成分四边形来表征Ｌａ，Ｃｅ，Ｎｄ和Ｐｒ的成分变化，在此基础上，作出合会的性能对稀土成分的分布图．根据该图，可选择适当的稀土成分，来获得性能优异的贮氢合金电极材料．

非化学计量比贮氢电极合金的电化学性能和结构及热力学研究

在分别优化稀土Ａ组元和过渡族Ｂ组元基础上，研究了ＡＢγ合金中化学计量比γ值对其电化学性能的影响。结果表明，超化学计量比（γ＝５．３）的合金具有较高的放电容量（２９５ｍＡ·ｈ／ｇ）和较小的循环容量衰退（电化学容量在２５０次循环后为８３．６％），但其大电流放电能力有所降低。经ＸＲＤ分析，γ＝５．３的合金具有最大的晶胞体积。从放电容量和循环寿命来看，超化学计量比合金优于化学计量比合金和欠化学计量比合金，但其高倍率放电能力有所降低。用Ｓｉｅｖｅｒｔ固——气吸放氢（ｐ－Ｃ－Ｔ）法求得吸放氢反应的ΔＨ和ΔＳ表明，超化学计量比合金ＡＢ５．３的生成热较负，形成的氢化物比较稳定，氢原子扩散困难，且使氢原子发生电化学氧化反应阻力增大，因而使电极合金的大电流放电能力降低。