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.     

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。     

低钴稀土系贮氢合金的研究

通过在稀土系贮氢合金中添加不同含量的Fe或Cu元素,部分替代合金中Co的方法,研究低钴贮氢合金电化学性能上的差异.结果表明:由于合金组成和化学计量比的不同,同样是添加了Fe或Cu的合金在电化学性能上表现不同,但总体说,含Cu低钴贮氢合金容量和倍率放电性能较好,含Fe低钴贮氢合金有较好的循环稳定性,过化学计量比的合金循环稳定性要好于欠化学计量比的合金.     

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.     

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。     

替代元素对低钴贮氢合金性能的影响

在AB5型贮氢合金MlNi3.55Co0.75Al0.3Mn0.4钴含量基础上,B侧采用Cu、Fe、Zn、Cr元素替代Co,A侧加入Dy来制备低钴贮氢合金.并对合金的放电容量、循环稳定性以及微观结构进行了研究分析.研究表明,通过调整合金成分可以使贮氢合金具有较好的组织均匀性和综合电化学性能.     

粉末冶金法制备La_(0.75)Mg_(0.25)Ni_(3.5-x)Mn_x(x=0-0.4)合金及其电化学贮氢性能研究

为了改善稀土系A_2B_7型贮氢合金的电化学贮氢性能,采用粉末冶金方法制备的La_(0.75)Mg_(0.25)Ni_(3.5-x)Mn_x(x=0,0.1,0.2,0.3,0.4)贮氢合金,研究少量Mn替代Ni对合金相结构和电化学性能的影响。结果表明:合金由La Ni5、La2Ni7两相组成,随着Mn含量的增加,两相晶胞逐渐膨胀。Mn的加入能显著改善合金的电化学性能,然而过高的Mn含量会对合金的放电性能带来不利影响。其中La_(0.75)Mg_(0.25)Ni_(3.2)Mn_(0.3)合金电极的最大放电容量为362.3m Ah/g,经过100次循环后容量保持率为69.5%。此外,合金电极的高倍率放电性能、线性极化曲线以及电化学交流阻抗谱的测试均表明合金的电化学动力学性能随着Mn含量的增加先增大而后减小。     

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.     

复相La-Mg-Ni系贮氢合金制备技术新进展

综述了近年来不同制备技术影响复相La-Mg-Ni系贮氢合金微观结构与电化学性能的研究现状,从合金的微观结构对其电化学参数起着决定性作用这一基点出发,比较了不同制备技术的优缺点,为选择具有优异电极性能贮氢合金的制备技术参数提供思路和依据。     

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.     

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...     

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.     

La0.8Mg0.2(Ni2.7Co0.6Al0.1Mn0.1)x贮氢合金的电化学性能分析

采用恒电位法、EIS分析及双电极系统对La0.8Mg0.2(Ni2.7Co0.6Al0.1Mn0.1)x(x=0.9～1.10)系列合金进行电化学性能分析。结果表明,x=1.05的合金具有较好的自放电性能(CR=97.3%),而x=1.10的合金有较高的电化学容量(369 mAh.g-1)。合金电极的电化学阻抗谱(EIS)表明,随着化学计量比x的增大,合金电极的电荷迁移电阻先减小后增大,动力学性能先增强后减弱。线性极化测试表明,随着化学计量比x的增大,合金电极表面的电化学反应速率先增大后减小。通过合金电极阳极电流对时间响应的半对数曲线计算的氢扩散系数D随着化学计量比x的增大先增大后降低,说明合金内部的氢扩散能力先增强后降低。     

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.     

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.     

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.     

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.     

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.