Effect of electrolyte concentration on low-temperature electrochemical properties of LaNi5 alloy electrodes at 233 K

The effect of KOH electrolyte concentration on low-temperature electrochemical properties of LaNi5 alloy electrodes at 233 K was studied. The results indicated that the electrolyte concentration had great influence on discharge capacity and discharge voltage plateau of LaNi5 alloy electrode at 233 K, and the highest discharge capacity and discharge voltage plateau were both obtained at 6 mol/L KOH. When the KOH electrolyte concentration changed from 5 to 9 mol/L at 233 K, the high rate discharge ability （HRD） had the same change tendency as the diffusion coefficient, but the exchange current density did not change significantly, which implied that hydrogen diffusion was the control step at low temperature 233 K for discharge process of LaNi5 alloy electrode.     

Effect of annealing temperature on microstructure and electrochemical performance of La0.75Mg0.25Ni3.5Co0.2 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.     

Phase Structure and Electrochemical Properties of RE-Mg Based Composite Hydrogen Storage Alloys

Rareearth basedAB5 typealloy ,akindofhy drogenstoragealloyusedasnegativeelectrodemateri alsofthenickel/metalhydride (Ni/MH )secondarybattery ,haseasyinitialactivation ,longcyclelifeandlowcost ,butstillasmalldischargecapacity ,poorhigh ratedischargeability(HRD)andpoorpropertiesatlowtemperature[1,2 ] .Therefore ,howtoincreaseitsdischargecapacityandtoimproveotherelectrochemi calpropertiesismeaningfulbothintheoryandinpracticalapplication .Mg basedhydrogenstorageal loysareremarkablebecauseofitsr…     

Ti-V基贮氢合金电极电化学性能的影响因素

研究了粉体粒度、导电镍粉及工作温度对合金电极Ti0.17Zr0.08V035Ni0.10Ni0.30放电性能的影响。结果表明：随着合金粒度的减小，放电容量有所增加，但放电容量随着循环数的增加而有所降低；而导电羰基镍粉含量的变化对合金电极的放电容量几乎没有影响。随着合金电极工作温度的增加，合金电极的循环稳定性、充、放电电压均有所降低。温度明显地影响Ti—V基贮氢合金电极中V在电介质溶液中的溶解。     

宽温型AB5储氢合金结构及其电化学性能研究

用高频感应熔炼法制备了Mm(NiCoAlMn)5储氢合金,采用模拟电池法测试了合金在238～323 K温度范围内的活化、放电容量和高倍率放电性能.结果表明:制备合金为典型AB5型储氢合金,303K温度条件下吸氢量达到1.38％(质量分数),氢化物生成焓为32.36 kJ ·mol-1H2.合金电极的活化性能、放电容量和高倍率性能受温度影响显著.室温预活化可有效改善电极的低温性能,经室温预活化后合金电极在238 K最大放电容量达到336 mAh·g -1,明显高于未经室温预活化的最大放电容量25 mAh·g-1.Mm(NiCoMn)5贮氢合金电极的高倍率性能随着温度的升高先升高后降低,273和303 K温度条件下合金保持高倍率性能良好,3C放电电流密度条件下容量保持率均高于80％;238 K温度条件下合金的大电流放电性能急剧降低,1C放电电流密度条件下容量保持率仅为10％; 273 K下合金电极的综合性能最佳,最大放电容量达到340 mAh·g-1,300 mA·g-1放电电流密度下的高倍率放电比率为86％.循环伏安法测试证实,在238～323 K范围内,电极的氧化峰峰值电流(Ip)与扫描速度的平方根(v1/2)之间均存在良好的线性关系,整个电极反应受氢原子扩散控制;随着温度的降低氢扩散系数急剧下降,从而导致该合金电极的低温高倍率放电性能变差.由Arrhenius公式计算出合金中的氢扩散活化能为10.56 kJ·mol -1.     

Application of Nanocrystalline LaNi5-type Hydrogen Absorbing Alloys in Ni-MHx Batteries

Duringlastyears ,interestinthestudyofnanos tructuredmaterialshasbeenincreasing .Thisisduetorecentadvancesinmaterials′synthesesandcharacteri zationtechniquesandtherealizationthatthesemateri alsexhibitmanyinterestingandunexpectedphysicalaswellaschemicalpropertieswithanumberofpoten tialtechnologicalapplications .Forexample ,hydrogenstoragenanomaterialsarethekeytothefutureofthestorageandbatteries/cellsindustries[1,2 ] .TheTiFe ,ZrV2 andLaNi5phasesarefamiliarmaterialswhichabsorblargequantitiesof…     

Effect of cobalt content on electrochemical performance of La-Mg-Ni system （Ce2Ni7-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.     

Effect of annealing treatment on hydrogen storage properties of La-Ti-Mg-Ni-based alloy

The present study dealt with investigations on the effects of annealing on the hydrogen storage properties of La 1.6 Ti 0.4 MgNi 9 alloys.The experimental alloys were prepared by magnetic levitation melting followed by annealing treatment.For La 1.6 Ti 0.4 MgNi 9 alloys,LaNi 5,LaNi 3 and LaMg 2 Ni 9 were the main phases,Ti 2 Ni phase appeared at 900℃.Annealing not only enhanced the maximum and effective hydrogen storage capacity,improved the hydrogen absorption/desorption kinetics,but also increased the discharge capacity.The cyclic stability had been improved markedly by annealing,e.g.,when the discharge capacity reduced to 60% of maximum discharge capacity,the charge/discharge cycles increased from 66(as-cast) to 89(annealed at 800℃) and 127 times(annealed at 900℃).La 1.6 Ti 0.4 MgNi 9 alloy annealed at 900℃ exhibited better electrochemical properties compared to the other two alloy electrodes.     

Effects of annealing on microstructures and electrochemical properties of La0.8Mg0.2Ni2.4Mn0.10Co0.55Al0.10 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 CHI 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.     

Initial Activation of Hydrogen-Storage Alloy Electrode by Chemical Modification

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Phase Structure and Electrochemical Properties of Rare Earth Based Hydrogen Storage Alloys

The rare earth based hydrogen storage alloys MmxM1 1 - x ( Ni3.55 Co0.75 Mn0.4 A10.3 ) ( x = 0 ～ 0.5 ) were investigated in this work.Adjusted Ml: Mm ratio to change the content of La,Ce,Pr and Nd in the alloys and then to change the phase structure, the influences of phase structure on the electrochemical properties were analyzed.The results indicate that the main phase of all alloys is LaNi5 with CaCu5 type structure and the crystal lattices constants of LaNi5 are changed with increasing x value, i.e, decreased a-axis, increased c-axis and axis ratio and nonlinear decreased crystal volume.The crystal volume of the alloy with x = 0.3 is larger than others.There is second phase A1LaNi4 in alloys when x≥0.3, which decrease the discharge capacity, but increase the cycling stability and high rate discharge ability.Compared comprehensively, the alloy with x = 0.3 shows the higher discharge capacity and the better cycling stability.     

镍氢电池在放电过程中的电极极化

利用暂态技术－电流阶跃法对镍氢电池的正负极在放电过程中的电化学极化、浓差极化及欧姆极化进行了研究。镍氢电池放电电压的衰减主要是由正极衰减引起的,浓差极化又是正极衰减的主要原因。负极的电化学极化和浓差极化随放电深度的增加而变化,但电化学极化增加的幅度较小。     

Co含量对La0.55Pr0.05Nd0.15Mg0.25Ni3.5-xCoxAl0.25（x=0～0.4）储氢合金电极性能的影响

采用电磁感应悬浮炉制备La0.55Pr0.05Nd0.15Mg0.25Ni3.5-xCoxAl0.25(x=0,0.1,0.2,0.3,0.4)系列合金,研究Co含量对合金的相结构、吸放氢性能和电化学性能的影响。研究结果表明,该系列合金主要由LaNi5、Nd2Ni7相组成。当Co含量大于0.2时,合金中出现La2Ni7相。压强-吸氢量-温度(Pressure-Content-Temprature)测试显示在303 K温度下,合金具有良好的吸氢性能,当x=0.4时合金的最大吸氢量为1.29(质量分数,%)。电化学测试表明:随x值变化,合金电极的最大放电容量分别为340.0(x=0.0)、346.6(x=0.1)、370.0(x=0.2)、320.0(x=0.3)和346.6(mA.h)/g(x=0.4);随Co含量增加,合金电极容量保持率不断增加,高倍率放电性能先增加后减小,循环伏安曲线、氢在合金体中的扩散系数D共同反映了合金电极的动力学特性。     

Se掺杂介孔二氧化锰的合成及电化学性能研究

以介孔硅SBA-15为模板,硝酸锰作锰源,采用液相浸渍法,合成了介孔二氧化锰;在合成的过程中掺入硒粉,制备硒掺杂的介孔二氧化锰。采用XRD、SEM、TEM和BET等分析手段对样品的形貌和结构进行表征。结果表明:所合成的介孔二氧化锰与SBA-15具有相似的形貌和有序介孔结构;掺杂硒后,介孔二氧化锰的形貌和结构都没有明显的变化。为了研究样品的电化学性能,在9 mol/L KOH溶液中,250 mA/g的电流密度下放电。结果表明:介孔二氧化锰的放电容量达到344.26 mAh/g,比EMD增加119.7%。掺杂硒后,介孔二氧化锰的放电容量增大了,当掺硒量为5%时,介孔二氧化锰的放电容量最大,达到430.25 mAh/g,比EMD增加174.6%。     

Study on Nanocrystalline Rare Earth Mg-Based System Hydrogen Storage Alloys with AB3-Type

A sort of rare earth Mg-based system hydrogen storage alloys with AB3-type was prepared by double-roller rapid quenching method. The alloys were nanocrystalline multi-phase structures composed of LaNi3 phase and LaNi5 phase by X-ray diffraction and scanning electron microscopy analyses, and the suitable absorption/desorption plateau was revealed by the measurement of P-C-I curve. Electrochemical studies indicate that the alloys exhibit good electrochemical properties such as high capacity and stable cycle life, and the discharge capacity is 369 mAh·g-1 at 0.2 C (72 mA·g-1), after 460 cycles, the capacity decay was only 19.4% at 2 C (720 mA·g-1).     

镍氢电池负极用低成本储氢合金的研究

研究了ABS型储氢合金在低Co含量条件下，随B组元替代元素Co，Al，Si等含量的变化对合金电化学性能的影响规律，同时研究了A组元中不同La／Ce比对合金电化学性能的影响情况。结果表明，随合金中Co含量的降低，合金的活化性能和放电容量得以改善，但合金的循环寿命下降也比较明显；在试验范围内，随Al元素的加入，合金的循环寿命得以改善，但材料的放电容量和活化性能均有所下降；随合金La／Ce比的降低，合金的放电容量略有下降，但其循环寿命和放电电压平台有较大提高。     

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.     

α型二氧化锰的制备及电化学性能研究

选用过硫酸钾(K_2S_2O_8)和一水合硫酸锰(MnSO_4·H_2O)为原材料,通过液相共沉淀法制得MnO_2,用X射线衍射和扫描电镜对制得的MnO_2进行结构形貌表征。结果表明,在控制溶液p H值为l,反应温度为60℃,反应时间为22 h的条件下,制得的四方晶系α-MnO_2微球的表面具有明显的纳米刺结构特征。将所制得的四方晶系α-MnO_2用于超级电容器的电极材料,以6 mol/L的KOH作为电解质溶液,研究其恒电流充放电、循环伏安及交流阻抗等电化学性能,当扫描速度为5 m V/s时,其比容量为156.0 F/g。     

Electrochemical properties of cobalt-free La0.80Mg0.20Ni2.85Al0.11M0.53 （M=Ni, Si, Cr, Cu, Fe） alloys

In order to investigate the effect of different B-site additions on phase structure and electrochemical properties of cobalt-free La-Mg-Ni based alloys, La0.80Mg0.20Ni2.85Al0.11M0.53 (M=Ni, Si, Cr, Cu, Fe) hydrogen storage alloys were prepared and studied systemati-cally. X-ray powder diffraction showed that the alloys consisted mainly of LaNi3 phase and LaNi5 phase except that Cr addition caused a minor Cr phase. Electrochemical testing indicated that alloys with additional Ni, Cr, Cu or Fe were activated within only 1-2 cycles, while that with Si addition needed 4 cycles. Adding Si, Cu and Fe increased cycling stability of La-Mg-Ni based alloys. However, maximum discharge capacity decreased from 362 mAh/g to 215 mAh/g in the order of Ni>Fe>Cu>Cr>Si. In addition, electrochemical kinetics of alloy electrodes was also researched by measuring high rate discharge ability (HRD), hydrogen diffusion coefficient (D) and limiting current density (IL).     

Co替代Ni对A2B7型贮氢电极合金相结构及电化学性能的影响

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xCox(x=0,0.25,0.75,1)四元贮氢合金,系统地研究了合金B侧Co对Ni部分替代对合金相结构及电化学性能的影响.X衍射(XRD)分析表明,La0.75Mg0.25Ni3.5-xCox由(La,Mg)2Ni-7相(包括Gd2 Co7型高温相和Ce2 Ni7型低温相)组成.此外,随着Co元素的加入,该类合金中出现CaCu5型LaNi5相.电化学测试表明,随Co含量的增加,合金电极活化次数增大,合金电极的最大放电容量增大,合金的最大放电容量由x =0.25时的376.53 mAh/g增加到x=1时的401.62mAh/g,氢扩散系数增大,循环稳定性变差,合金的高倍率放电性能降低,Co含量对合金电极高倍率放电性能HRD值的影响与对合金电极交换电流密度的影响趋势一致,这表明电极合金表面的电化学反应对合金的动力学性能影响更大.