机械合金化MlNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3)/Mg复合储氢合金的相结构和电化学性能

采用机械合金化法制备了MlNi3.55Co0.75Mn0.4Al0.3+x%Mg(Ml=富镧混合稀土;x=3,5,7,10)复合储氢合金。利用X射线衍射和电化学测试方法对MlNi3.55Co0.75Mn0.4Al0.3铸态合金和MlNi3.55Co0.75Mn0.4Al0.3/Mg复合合金的相结构和电化学性能进行了研究。X射线衍射结果发现,MlNi3.55Co0.75Mn0.4Al0.3合金由单一的La Ni5相组成。而MlNi3.55Co0.75Mn0.4Al0.3/Mg复合合金由La Ni5主相和小量的(La,Mg)2Ni3相组成,且合金中(La,Mg)2Ni3相的含量随镁含量x的增大而增多。此外,当复合合金中镁含量较多(x=10)时,复合合金有非晶化的趋势。电化学性能测试结果发现,当添加镁含量较少(x≤7)时,合金的最大放电容量、放电性能以及循环稳定性都好于MlNi3.55Co0.75Mn0.4Al0.3合金的相应性能,其中x=5时,合金的综合电化学性能最佳。合金电化学性能的改善得益于合金中形成恰当比例的La Ni5和(La,Mg)2Ni3相。     

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.     

铝在新型稀土镁基AB3型贮氢电极合金中的作用研究

借助于自制的开口式H型玻璃三电极测试体系，并在大量的前期实验工作基础上，研究了新型稀土镁基AB3型贮氢电极合金的性能以及添加Al的作用。发现用适量Al替代Ni可降低稀土镁基AB3型合金La0.7Mg0.3（Ni0.85Co0．15）3.5的氢化反应焓变和气态放氢平台压力，使合金氢化物变得更稳定；同时，使合金电化学循环100周期的容量保持率从63．8％提高到90．6％，有效解决了合金放电容量迅速衰减的难题；但Al的添加也降低了合金的最大放电容量、倍率放电性能和活化性能。     

快淬对La0.67Mg0.33(NiCo)3贮氢合金电化学性能的影响

测试了AB3型贮氢合金La0.67Mg0.33(NiCo)3铸态与快淬态的电化学性能,用XRD和SEM测试了合金的微观结构,研究了快淬对AB3型贮氢合金电化学性能的影响.结果表明,快淬使合金的放电容量降低,对合金的活化性能没有明显影响;快淬降低了合金的容量衰减率,提高了合金的循环寿命,其主要原因是快淬使合金的晶粒显著细化.铸态和快淬态合金均具有多相结构,包括斜六面体的(La,Mg)Ni3相,六方的LaNi5相及少量的LaNi2相.快淬使合金中的LaNi2相含量增加,这是快淬使合金放电容量下降的一个主要原因.     

化学计量比对AB5型贮氢合金相结构及电化学性能的影响

对低钴稀土系贮氢合金Ml(Ni0.78Co0.08Al0.06Mn0.08)x(4.8≤x≤5.4)的相结构及电化学性能进行了研究.结果表明在4.8≤x≤5.2的合金中除CaCu5型结构的主相之外,还出现LaNi3第二相,而且合金中第二相(LaNi3)的析出量随着x值的增大而减少,化学计量比x=5.4的合金则有富镍相析出,B侧合金化使低钴贮氢合金形成单相AB5型合金的化学计量比由x=5.0增大至5.2～5.4之间.四种不同化学计量比合金的活化性能都较好,合金的最大放电容量随化学计量比x的增大而增加,过化学计量比(x=5.4)合金具有最大的放电容量,最优的放电电压特性及最佳的循环稳定性,且其高倍率放电性能也较好.     

热处理对La0.65Pr0.05Nd0.05Mg0.25Ni3.3Al0.1储氢合金结构和电极性能的影响

为了了解新型稀土-镁-镍系储氢合金的结构和电化学性能与热处理温度的关系,通过中频感应熔炼法制备了La0.65Pr0.05Nd0.05Mg0.25Ni3.3Al0.1储氢合金,在氩气保护下进行退火热处理,温度为1123K、1173K和1223K,保温时间8h.应用X射线衍射、扫描电镜、能谱分析等方法研究了合金的结构,测试了合金的主要电化学性能.结果表明该合金由三相组成(La,Mg)Ni3.5相、LaNi5相和(La,Mg)Ni2相,退火后三相的相对含量发生了变化, 随着热处理温度的逐步提高,合金中LaNi5相和(La,Mg)Ni2相的比例减小,(La,Mg)Ni3.5相的比例增加.合金的放电容量、充放电循环稳定性与合金组成相所占比例密切相关, 尤其是(La,Mg)Ni2相的存在不容忽视.     

不同化学计量比稀土镁基贮氢电极合金结构和电化学性能

用冷坩锅磁悬浮熔炼的方法制备了不同化学计量比的La0.7Mg0.3(Ni0.85Co0.15)x(x=3.0,3.1,3.2,3.3,3.4,3.5)稀土镁基贮氢电极合金,采用X射线衍射和三电极测试体系研究了合金的相结构和电化学性能。X射线衍射分析结果表明,该系列合金均由(La,Mg)Ni3相、(La,Mg)2Ni7相、LaNi5相及少量杂质相组成,为多相结构;随着化学计量比x的增加,(La,Mg)Ni3相的含量降低,相应LaNi5相的含量增加。电化学测试结果表明,该系列合金的最大放电容量均高于目前已商品化的稀土基AB5型贮氢电极合金的最大放电容量(310~330 mAh.g-1),且当x=3.4时,合金的最大放电容量可达395.4 mAh.g-1,较AB5型合金高约30%,是合金中各相的含量比例较为合适的结果;该系列合金活化性能、倍率放电性能良好,并随着化学计量比x的增加得到进一步改善,这与同时作为贮氢相和催化相的LaNi5相含量的增加有关;在电化学吸放氢循环过程中,合金的循环稳定性较差,有待进一步提高。     

A2B7型La0.75Mg0.25Ni3.5-xFex(x=0～0.3)贮氢合金相结构及电化学性能研究

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xFex(x=0.0.05,0.1,0.2,0.3)四元贮氢合金,系统地研究了合金B侧Fe对Ni部分替代对合金相结构及电化学性能的影响.X射线衍射(XRD)分析表明,La0.75Mg0.25Ni3.5-xFex由(La,Mg)2Ni7相(包括Gd2Co7型高温相和Ce2Ni7型低温相)组成.此外,随着Fe元素的加入,该类合金中出现CaCu5型LaNi5相,且随着Fe含量的增加而增多.电化学测试表明,随Fe含量的增加,合金电极活化次数变化不大,而其最大放电容量呈现先增后减的趋势,合金的最大放电容量由x=0.05时的376.21 mAh·g -1下降到x=0.3时的340.89 mAh·g-1;合金的高倍率放电性能随着Fe含量的增加而降低,当电流密度为900 mA·g-1时,合金的高倍率放电性能由83.66%(x=0)减小到62.23%(x=0.3);循环稳定性先增加后下降.     

制备工艺对La_(0.80)Mg_(0.20)Ni_(3.75)合金电极性能的影响

采用中频感应真空熔炼(IM)和放电等离子烧结(SPS)工艺制备La0.80Mg0.20Ni3.75合金。XRD分析表明,这两种工艺制备的合金均含有LaNi5和(La,Mg)2Ni7主相,而中频感应真空熔炼法制备的合金(IMLa合金)还含有(La,Mg)Ni3相,放电等离子烧结法制备的合金(SPSLa合金)还含有Ni及La2Mg17相。电化学性能测试结果表明,作为镍氢电池负极材料,IMLa合金的放电容量、损耗角及极限电流密度均较大;而SPSLa合金的循环性能较好,这归因于SPSLa合金晶粒细小,组织均匀,Ni和La2Mg17相弥散分布,可减弱其电极脱落程度。     

低钴AB5型贮氢合金的制备与研究

用均匀设计试验方法设计系列含Fe低Co AB5型贮氢合金B侧配比, 以放电容量、活化次数、容量保持率及放电平台中值电位为多目标函数, 采用逐步回归分析方法和最小二乘法及黄金分割一维寻优手段进行最优化处理, 确定了最优化的B侧合金元素的摩尔比 Mm0.8La0.2Ni4.0Mn0.5Al0.3Co0.37Fe0.13(AB5.3).新型含Fe低Co MmB5型贮氢合金是单相CaCu5型结构, Co含量为4.97%, 放电容量达307.3 mAh·g-1(极片), 活化次数为两次, 500次循环后容量保持率为78.9%, 高温容量为277.2 mAh·g-1(55 ℃), 低温容量为197.3 mAh·g-1(-30 ℃), 3C放电容量为275.4 mAh·g-1.     

Electrochemical Properties of Silicon Doped MlNi5 Type of Hydrogen Storage Alloys

ＴｈｅＬａＮｉ5 ｂａｓｅｄｈｙｄｒｏｇｅｎｓｔｏｒａｇｅａｌｌｏｙｓａｒｅｐｒｏｍｉｓｉｎｇｎｅｇａｔｉｖｅｅｌｅｃｔｒｏｄｅｍａｔｅｒｉａｌｓｆｏｒｒｅｃｈａｒｇｅａｂｌｅＮｉ/ＭＨｂａｔｔｅｒｉｅｓｂｅｃａｕｓｅｔｈｅｙｐｏｓｓｅｓｓａｈｉｇｈｃａｐａｃｉｔｙａｎｄａｒｅｅａｓｙｔｏａｃｔｉ ｖａｔｅ .ＢｕｔｔｈｅｄｉｓｃｈａｒｇｅｃａｐａｃｉｔｙｏｆｔｈｅＬａＮｉ5ｅｌｅｃｔｒｏｄｅｄｅｃｌｉｎｅｓｒａｐｉｄｌｙｄｕｒｉｎｇｃｈａｒｇｅ ｄｉｓ ｃｈａｒｇｅｃｙｃｌｅｓ (5 0 %ｏｆｔｈｅｃａｐａ…     

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.     

A study on hydrogen storage and electrochemical properties of La_（0.55）Pr_（0.05）Nd_（0.15）Mg_（0.25）Ni_（3.5） （Co_（0.5）Al_（0.5））_x （x=0.0, 0.1, 0.3, 0.5） alloys

The La0.55Pr0.05Nd0.15Mg0.25Ni3.5(Co0.5Al0.5)x(x=0.0, 0.1, 0.3, 0.5) alloys were prepared by magnetic levitation melting under an Ar atmosphere, and the effects of Co and Al on the hydrogen storage and electrochemical properties were systematically investigated by pressure composition isotherms, cyclic voltammetry, Tafel polarization and electrochemical impedance spectroscopy testing. The results showed that the alloy phases were mainly consisted of (La,Pr)(Ni,Co)5, LaMg2Ni9, (La,Nd)2Ni7 and LaNi3 phases, and the cell volumes of (La,Pr)(Ni,Co)5, LaMg2Ni9, (La,Nd)2Ni7 and LaNi3 phases expanded with Co and Al element added. The hydrogen storage capacity initially increased from 1.36 (x=0) to 1.47 wt.% (x=0.3) and then decreased to 1.22 wt.% (x=0.5). The discharge capacity retention and cycle stability of the alloy electrodes were improved with the increase of Co and Al contents. The La0.55Pr0.05Nd0.15Mg0.25Ni3.5(Co0.5Al0.5)0.3 alloy electrode possessed better electrochemical kinetic characteristic.     

AB5型储氢合金性能波动的原因探析

通过研究稀土原料中的杂质及合金的微观组织,探讨了用感应炉批量生产ＡＢ５型储氢合金性能波动的可能原因。储氢合金的性能由合金的成分、微观组织和表面状态决定。合金性能波动除受浇铸时的冷却条件影响外,还与稀土原料中铁、镁等杂质及熔炼工艺因素有关。     

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.     

Effects of Fe-substitution for cobalt on electrochemical properties of La-Mg-Ni-based alloys

In order to improve electrochemical properties,especially cycling stability,Co was partially substituted by Fe in A2B7-type La-Mg-Ni-based alloys.The La0.74Mg0.26Ni2.55Co0.65-xFex(x=0,0.10,0.20,0.30) alloys were prepared by inductive melting,and their phase structure and electrochemical properties were studied.The XRD and SEM results showed that the alloys consisted mainly of(La,Mg)2Ni7 phase,(La,Mg)5Ni19 phase and LaNi5 phase,except for absence of LaNi5 phase in the non-substituted alloy.The(La,Mg)5Ni19 ph...     

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.     

Phase Structure and Electrochemical Characteristics of Ml（Ni3.55Co0.75Mn0.40Al0.30）5x （x=0.88, 0.92, 0.96, 1.00） Hydrogen Storage Alloys

The phase structure and electrochemical characteristics of Ml （（Ni3.55Co0.75Mn0.40Al0.30）sx （ x = 0.88, 0.92, 0.96, 1.00） hydrogen storage alloys were studied. The effect of the stoichiometric ratio on the phase structure and electrochemical characteristics was analyzed. The results of XRD reveal that all the alloys consist mainly of LaNi5 phase with the hexagonal CaCu5 structure. But a few of the diffraction peaks of La2Ni7 phase on XRD pattern are observed when x ≤ 0.92, and with decreasing x, the intensity of La2Ni7 diffraction peaks increases and the values of lattice parameters a and cell volume increase, c and c/a of LaNi5 phase decrease gradually. When x≥0.96, La2Ni7 phase disappears and the alloys become single CaCu5-type. The electrochemical tests show that the maximum discharge capacity, high rate dischargeability and low temperature dischargeability are improved to different degrees by adjusting the stoichiometric ratio.     

Effect of Ni/（La＋Mg） Ratio on Structure and Electrochemical Performance of La-Mg-Ni Alloy System

As the alloy with the most suitable Ni/(La+ Mg) ratio has higher capacity and good cycle stability,theeffects of Ni/(La+Mg) ratios on the electrochemical performances of the La0.80 Mg0.20 Nix (x= 3.5 to 5.0) alloys have been investigated to find the most suitable Ni/(La+ Mg) ratio.The results of XRD and SEM observations show that the phase composition of the alloys varies with different Ni/(La+Mg) ratios.When Ni/(La+Mg) is notmore than 4.25,all the alloys contain LaNi5 and (La,Mg)2Ni7 phases,in addition,the LaMg and (La,Mg)Ni3 phases exist in the x=3.5 and 3.75 alloys,respectively.The LaMg2Ni9 phase exists in the x=4.25 alloy.There are the LaNi5 and LaMg2 Ni9 phases in the x= 4.5,4.75,and 5.0 alloys.The phase abundance and cell volume change with different Ni content.When the Ni/(La+Mg) ratio is not more than 4.25,the alloys possess excellent activation capability,however,the activation capabilities of the alloys decrease with a further increase in the Ni/(La+Mg)ratio.With increasing the Ni/(La+ Mg) ratio,the maximum discharge capacities,the medium voltages,and the cycle stabilities of the alloys first increase and then decrease.When the Ni/(La+Mg) ratio is 3.75,the corresponding alloyhas the maximum discharge capacity among all the alloys.However,the cycle stability of the Ni/(La+ Mg)= 4.0 alloy is better than that of the others.