快淬纳米晶/非晶Mg2-xLaxNi (x=0～0.6)合金的贮氢动力学

为了改善Mg2Ni型合金气态及电化学贮氢动力学性能,用La部分替代合金中的Mg,用快淬技术制备了Mg2-xLaxNi(x=0,0.2,0.4,0.6)合金,用XRD,SEM,HRTEM分析了铸态及快淬态合金的微观结构;用自动控制的Sieverts设备测试了合金的气态贮氢动力学性能,用程控电池测试仪测试了合金的电化学贮氢动力学.结果发现,快淬无La合金具有典型的纳米晶结构,而快淬含La合金显示了以非晶相为主的结构,表明La替代Mg提高Mg2Ni型合金的非晶形成能力.La替代Mg明显地改变Mg2Ni型合金的相组成.当La替代量x=0.4时,合金的主相改变为(La,Mg) Ni3+ LaMg3.合金的气态及电化学吸放氢动力学对La含量及快淬工艺敏感,La替代使合金的吸氢动力学降低,但适量的La替代可以明显改善合金的放氢动力学及高倍率放电能力.适当的快淬处理可以提高合金的气态及电化学贮氢动力学,但获得最佳贮氢动力学的快淬工艺与合金的成分密切相关.     

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。     

AB5型与AB3.5型贮氢合金的电化学性能对比研究

为了对比研究AB5型与AB3.5型贮氢合金的电化学及动力学特性,以AB5型MlNi3.68Mn0.32Co0.73Al0.27和AB3.5型Ml0.80Mg0.20 （NiMnAlCu）3.6、La0.6 Mg0.4 Ni3.5为研究对象.采用XRD分析了合金的相结构,利用电化学方法测试合金的电化学及动力学特性.结果发现,MlNi3.68 Mn0.32Co0.73Al0.27合金由单相LaNi5相组成,而Ml0.80Mg0.20（NiMnAlCu）3.6、La0.6Mg0.4Ni3.5均有LaNi5相和La2Ni7相组成.AB3.5型合金的放电容量、荷电保持率以及动力学特性高于AB5型合金.     

快淬 TiZrVMnNi 贮氢合金的电化学性能研究

对比研究了熔体旋转和常规铸态Ti0 .8Zr0 .2 Mn0 .5V0 .5Ni1.0 贮氢合金的电化学特性。发现快淬态与铸态合金的活化性能都很好 ,经过 1～ 3次充放电循环 ,就可达到最大放电容量。快淬工艺明显提高了合金的放电容量 ,并且淬速与放电容量之间在一定情况下出现峰值。快淬工艺同时改善合金的放电电压特性 ,使合金的放电平台更平 ,平台电压更高。但是快淬钛基贮氢合金的循环稳定性能和铸态合金一样差 ,放电容量在 10次内急剧衰减。     

RE(RE=Nd,Sm,Pr)部分替代La对A_2B_7型合金电化学贮氢性能的影响

La-Mg-Ni系A2B7型合金由于其高的放电容量被认为是最具希望的Ni-MH电池负极材料,然而,低的电化学循环稳定性制约着合金的实际应用。为了改善La-Mg-Ni系A2B7型合金的电化学贮氢性能,用RE(RE=Nd,Sm,Pr)部分替代合金中的La,用感应熔炼及退火工艺制备了La0.8-xRExMg0.2Ni3.35Al0.1Si0.05(RE=Nd,Sm,Pr;x=0,0.2)电极合金。为了抑制Mg在熔炼过程中的挥发,熔炼过程中采用氦气作为保护气氛。用X射线衍射(XRD)和扫描电镜(SEM)分析了铸态及退火态合金的微观结构,并测试了铸态及退火态合金的电化学贮氢性能,比较了不同稀土元素替代La对合金电化学性能的影响。结果表明,铸态及退火态合金包含两个主相,具有Ce2Ni7型结构的(La,Mg)2Ni7相以及Ca Cu5型结构的La Ni5相。RE(RE=Nd,Sm,Pr)部分替代La未影响合金的相组成,但使合金的相含量发生明显改变。此外,元素替代使铸态及退火态合金的组织明显细化。RE(RE=Nd,Sm,Pr)部分替代La显著改善了合金的电化学贮氢性能,包括电化学循环稳定性、放电容量及电化学动力学性能。     

制备工艺对无钴AB5型贮氢合金的相结构和电化学性能的影响

用真空熔炼、快淬工艺以及球磨工艺制备稀土基无钴AB5型La（NiMnAlFe）5贮氢合金，用XRD测试了合金的相结构，并测试了不同制备工艺下合金的电化学性能。研究了制备工艺对无钴合金的相结构和电化学性能的影响。结果表明，由真空熔炼和快淬工艺制备的合金为CaCu5型单相结构，球磨合金由CaCu5型相和游离Ni相组成，并出现了非晶化趋势。快淬和球磨均使合金的放电容量降低，循环稳定性提高，但球磨工艺的影响更为显著，主要原因是球磨后合金中出现非晶化趋势。     

铸态及快淬态Mm(NiCoMnAl)_5-Mg_2Ni储氢合金的微结构与电化学性能

首先采用二步熔炼法制备了铸态Mm(NiCoMnAl)_5-Mg_2Ni复合储氢合金,然后在不同快淬速度下对铸态Mm(NiCoMnAl)_5-Mg_2Ni复合合金进行快淬处理,获得一系列不同快淬速度的快淬态Mm(NiCoMnAl)_5-Mg_2Ni复合储氢合金。利用X射线衍射(XRD)、扫描电镜及能谱分析(SEM/EDS)和电化学测试方法研究了所有合金的微结构和电化学性能。微结构分析表明,铸态Mm(NiCoMnAl)_5-Mg_2Ni复合合金由LaNi_5和少量的Mg_2Ni相组成。而铸态复合合金经快淬处理后,合金中少量的Mg_2Ni相消失,同时有LaNi_3和极少量的La2Ni3新相形成。快淬态合金中的Mg元素主要以固溶形式优先存在于富稀土LaNi_3相中,形成(La,Mg)Ni_3相。电化学分析表明,恰当的快淬处理能使Mm(NiCoMnAl)_5-Mg_2Ni复合合金的活化性能、最大放电容量、放电特性和循环稳定性得到改善。但快淬速度太大,上述性能均有变坏趋势。当快淬速度为15 m·s-1时,Mm(NiCoMnAl)_5-Mg_2Ni复合合金具有最大的放电容量,此时合金的最大放电容量为303.5 m Ah·g~(-1),比铸态合金的最大放电容量增大了3.3%;快淬速度为20 m·s~(-1)时,复合合金的循环稳定性最佳,80次循环后的容量保持率为98.3%,比铸态合金的容量保持率增大了11.9%。     

快淬对合金Mm(NiCoMnAl)5.1B0.1组织及电化学性能的影响

对铸态和快淬态贮氢合金Mm(NiCoMnAl)5.1B0.1的微观组织和电化学性能进行了研究。发现快淬态合金基本上消除了第二相，快淬合金组织中存在一定比例的非晶相，并且随着淬速增加非晶相的量增多；与铸态合金相比，快淬态合金的放电容量有所降低，但循环寿命显著提高，这主要是由于快淬导致晶粒细化和形成一定数量的非晶态组织。     

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。     

Effect of Rapid Quenching on Microstructures and Electrochemical Performances of La2Mg（Ni0.85Co0.15）9M0.1 （M = B, Cr） Hydrogen Storage Alloys

The La-Mg-Ni-system （PuNi3-type） La2Mg （Ni0.85 Co0.15 ）9M0.1 （ M = B, Cr） hydrogen storage etectrode alloys were prepared by casting and rapid quenching. The electrochemical performances and microstructures of the as-cast and quenched alloys were determined and measured. The effects of rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The obtained results show that the alloys are composed of the （La, Mg） Ni3 phase （PuNi3-type structure） and the LaNi5 phase, as well as the small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast alloy containing boron, and the Ni2B phase in the alloy nearly disappears after rapid quenching. The relative amount of each phase in the alloys depends on the quenching rate. The rapid quenching technique can greatly improve the electrochemical performance of the alloy, and the effect of rapid quenching on the activation performances of the alloys is minor. Rapid quenching enhances the cycle stability of the alloy, and the cycle life of the alloy increases with the increase of the quenching rate.     

Relations between Quenching Rate and Electrochemical Characteristics of Mm (NiCoMnA1) 5Bx (x=0～0.2) Electrode Alloys

Low-Co AB5-type Mm(NiCoMnA1)5Bx (x = 0, 0.1, 0.2 ) electrode alloys were prepared by casting and rapid quenching.The effects of the rapid quenching on the lattice constants, microstructures and electrochemical characteristics of the alloys were investigated in detail.The obtained results show that the rapid quenching made lattice constants and cell volume increased.In a range of the quenching rate, rapid quenching can increase the discharge capacities of the alloys.However, the discharge capacity of the as-quenched alloy is lower than that of the as-cast alloy when quenching rate is more than a critical value.The cycle lives of the alloys increase monotonously with the increase of the quenching rate.     

Effect of rapid solidification treatment on structure and electrochemical performance of low-Co AB5-type hydrogen storage alloy

The effect of rapid solidification on structure and electrochemical performance of the LaNi4.5Co0.25Al0.25 hydrogen storage alloy was investigated by X-ray powder diffraction and a simulated battery test, including maximum capacity, cycling stability, self-discharge, and high-rate discharge ability （HRD）. All the melt-spun alloys were single-phase with the CaCu5-type structure （space groupP6/mmm）. In comparison to the as-cast alloy, the rapidly quenched alloys manifested an improved homogeneity of com-position and expanded lattice parameters. The electrochemical measurements showed that the activation property, cycling stability and self-discharge of the alloy electrodes were also improved for the rapid solidified alloys. The HRDof the as-cast alloy was better than those of all the rapidly solidified alloys. As the quenching rate increased, the HRD and exchange current density first decreased and then increased.     

Influence of rapid quenching on cyclic stability of La-Mg-Ni system （AB3-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.     

Structure and electrochemical hydrogen storage characteristics of the as-cast and annealed La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 （x=0-0.4） alloys

In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4) elec-trode alloys were fabricated by casting and annealing. The microstructures of the as-cast and annealed alloys were characterized by XRD and SEM. The electrochemical hydrogen storage characteristics of the as-cast and annealed alloys were measured. The results revealed that all of the experimental alloys mainly consisted of two phases: (La,Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. As Sm content grew from 0 to 0.4, the discharge capacity and the high rate discharge ability (HRD) first in-creased and then decreased for the as-cast and annealed alloys, whereas the capacity retaining rate (S100) after 100 cycles increased continuously.     

La15Fe77-xNixMn5B3（x=55,60,65,70,75）储氢合金的结构与电化学性能研究

用熔炼-快淬工艺制备La15Fe77-xNixMn5B3(x=55,60,65,70,75)储氢电极合金。采用XRD、SEM、EDS及电化学方法研究合金的组织结构、放氢平台特性和电化学性能。研究结果表明,La15Fe77-xNixMn5B3(x=55,60,65,70,75)合金均为多相结构,主相是LaNi5相,另外还有(Fe,Ni)相和La3Ni13B2相。随Ni含量增加,合金电极的最大放电容量逐渐增加,活化次数明显减少,放氢平台特性变好,高倍率放电性能明显改善。     

Influence of magnesium content on structure and electrochemical properties of La_(1-x)Mg_xNi_(1.75)Co_(2.05) hydrogen storage alloys

La_(1-x)Mg_xNi_(1.75)Co_(2.05)(x=0.07, 0.08, 0.10, 0.13, 0.15) alloys were prepared by high-frequency inductive method, and then their structure and electrochemical properties were investigated systematically. The XRD analysis revealed that the alloys consisted of LaNi_5 phase and La_4MgNi_(19)(Ce_5Co_(19) + Pr_5Co_(19)) phase, and the introduction of Mg could promote the formation of La_4MgNi_(19) phase. The observation of microstructure showed that all the alloys processed dendritic structure, which was refined with the increase of x value. The electrochemical measurements showed that all the alloys could be activated within 2 cycles, and with increasing x, the maximum discharge capacity obviously increased from 254.00 m Ah/g(x=0.07) to 351.51 mAh/g(x=0.15), but the cycling stability(S_(80)) decreased somehow from 78.4% to 73.9%. Meanwhile, the appropriate addition of Mg could improve the high-rate discharge capacity(HRD) of the alloy electrodes, which was mainly controlled by the electrochemical reaction rate on the surface of the alloys.