Effects of rapid quenching on microstructures and electrochemical properties of La_(0.7)Mg_(0.3)Ni_(2.55)Co_(0.45)B_x(x=0-0.2) hydrogen storage alloy

1 Introduction Ni-MH batteries have been used widely by virtue of several of their advantages, such as high capacity, capable of performing a high rate charge/discharge, high resistance to overcharging and over-discharging, a long cycle life, environment…     

Structures and electrochemical performances of La_(0.75-x)Zr_xMg_(0.25)Ni_(3.2)Co_(0.2)Al_(0.1) (x=0-0.2) electrode alloys prepared by melt spinning

The La-Mg-Ni system A2B7-type electrode alloys with nominal composition La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1(x=0,0.05, 0.1,0.15,0.2)were prepared by casting and melt-spinning.The influences of melt spinning on the electrochemical performances as well as the structures of the alloys were investigated.The results obtained by XRD,SEM and TEM show that the as-cast and spun alloys have a multiphase structure,consisting of two main phases(La,Mg)Ni3 and LaNi5 as well as a residual phase LaNi2.The melt spinning leads to an obvious increase of the LaNi5 phase and a decrease of the(La,Mg)Ni3 phase in the alloys.The results of the electrochemical measurement indicate that the discharge capacity of the alloys(x≤0.1)first increases and then decreases with the increase of spinning rate,whereas for x0.1,the discharge capacity of the alloys monotonously falls.The melt spinning slightly impairs the activation capability of the alloys,but it significantly enhances the cycle stability of the alloys.     

Effects of rapid quenching on structure and electrochemical characteristics of La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx （x=0-0.4） electrode alloys

The La-Mg-Ni system PuNi3-type La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx (x=0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the rapid quenching on the structure and electrochemical characteristics of the alloys were studied. The results obtained by XRD, SEM and TEM indicate that the as-cast and quenched alloys mainly consist of two major phases, (La,Mg)Ni3 and LaNi5, as well as a residual phase LaNi. The rapid quenching does not exert an obvious influence on the phase composition of the alloys, but it leads to an increase of the LaNi5 phase and a decrease of the (La, Mg)Ni3 phase. The as-quenched alloys have a nano-crystalline structure, and the grain sizes of the alloys are in the range of 20-30 nm. The results by the electrochemical measurements indicate that both the discharge capacity and the high rate discharge(HRD) ability of the alloy first increase and then decrease with the variety of quenching rate and obtain the maximum values at the special quenching rate which is changeable with the variety of Mn content. The rapid quenching significantly improves the cycle stabilities of the alloys, but it slightly impairs the activation capabilities of the alloys.     

铸态及快淬态La2Mg（Ni0.85Co0.15）9Crx（x=0～0.2）电极合金的微观结构及电化学性能

为了提高La-Mg-Ni系（PuNi3）型贮氢合金的电化学循环稳定性,在La2Mg（Ni0.85Co0.15）9合金中加入微量Cr,用铸造及快淬工艺制备了La2Mg（Ni0.85Co0.15）9Crx（x=0,0.1,0.2）贮氢合金.分析测试了铸态及快淬态合金的电化学性能及微观结构,研究了Cr对铸态及快淬态合金微观结构及电化学性能的影响.结果表明,铸态及快淬态合金具有多相结构,包括（La,Mg）Ni3相（PuNi3结构））,LaNi5相和一定量的LaNi2相.快淬对合金的相组成没有影响,但使合金的相丰度产生变化.Cr的加入提高了铸态及快淬态合金的循环稳定性,但使合金的容量下降.合金的循环寿命随淬速的增加而增加,铸态及快淬态合金均有优良的活化性能.     

快淬La—Mg—Ni系贮氢合金的电化学性能及微观结构

采用铸造及快淬工艺制备了La—Mg-Ni系（PuNi3型）贮氢合金La0.7Mg0.3Ni2.55-Co0.45Cux（x=0～0．4），分析测试了铸态及快淬态合金的电化学性能与微观结构，研究了Cu替代Ni及快淬工艺对合金微观结构及电化学性能的影响。结果表明：铸态及快淬态合金具有多相结构，包括（La，Mg）Ni3相和LaNi5相和一定量的LaNi2相。快淬处理对合金的相组成没有影响，但使合会的衍射峰趋于均匀一致。Cu替代Ni使合金的电化学容量下降，但使合金的循环稳定性及放电电压特性得到改善。快淬可提高合金的循环稳定性，但使合金的容量下降。     

La0.7Mg0.3Ni2.55-xCo0.45Alx(x=0～0.4)贮氢合金的循环稳定性

为了提高La-Mg-Ni系贮氢合金的循环稳定性,以Al部分替代Ni,采铸造及快淬工艺制备了La0.7Mg0.3Ni2.55-xCo0.45Alx(x=0,0.1,0.2,0.3,0.4)电极合金,研究了Al替代量及快淬工艺对合金微观结构及电化学循环稳定性的影响。X射线衍射分析结果表明:铸态及快淬态合金具有多相结构,包括(La,Mg)Ni3相、LaNi5相和一定量的LaNi2相;Al替代使铸态合金中LaNi2相的量显著增加,但对快淬态合金中LaNi2相的相丰度影响不显著。电化学测试结果表明:随Al替代量的增加,合金的循环寿命大幅度提高;快淬处理可以提高合金的循环寿命,但随Al替代量的增加,淬速对循环寿命的影响减小。     

快淬工艺对La-Mg-Ni系贮氢合金微观结构及电化学性能的影响

用铸造及快淬工艺制备了La-Mg-Ni系（PuNi3型）贮氢合金La2Mg（Ni0．85Co0.15）9Bx（x=0，0．1，0．2），分析测试了铸态及快淬态合金的微观结构与电化学性能，研究了硼及快淬工艺对合金微观结构及电化学性能的影响。结果表明，铸态合金具有多相结构，主相包括（La，Mg）Ni3相（PuNi3型）和LaNi5相，残余相为一定量的LaNi2相和微量的Ni2B相，经快淬处理后Ni2B相消失，并且其它相的相对量随淬速的变化而变化。不含硼合金的容量随淬速的增加而单调减小，含硼合金的容量随淬速变化有一个极大值。合金的循环寿命随淬速的增加而增加，铸态及快淬态合金均有优良的活化性能。     

Improved Cycle Stability of La0.75-xPrxMg0.25Ni3.2Co0.2Al0.1 (x=0-0.4) Electrode Alloys by Melt Spinning

为了改善 La-Mg-Ni 系 A2B7型电极合金的电化学循环稳定性,用 Pr 部分替代合金中的 La,并用熔体快淬工艺制备了La0.75-xPrxMg0.25Ni3.2Co0.2Al0.1(x = 0, 0.1, 0.2, 0.3, 0.4)电极合金。用 XRD、SEM、TEM 分析了铸态及快淬态合金的微观结构。结果表明,铸态及快淬态合金均具有多相结构,包括 2 个主相(La,Mg)Ni3及 LaNi5和 1 个残余相 LaNi2。熔体快淬导致 LaNi5相增加而(La,Mg)Ni3相减少。电化学测试结果表明,熔体快淬显著地提高合金的电化学循环稳定性。当淬速从 0 m/s (铸态被定义为淬速 0 m/s)增加到 20 m/s 时,x=0 合金 100 次充放循环后的容量保持率从 65.32%增加到 73.97%,x=0.4 合金的容量保持率从 79.36%增加到 93.08%。     

La0.67Mg0.33Ni3.0-xAlx（x=0.0-0.35）贮氢合金相结构和电化学性能研究

采用X射线衍射、电子探针和电化学测试研究了La0.67Mg0.33Ni3.0-xAlx（x=0.0-0.35）合金的相结构和电化学性能。XRD结果和EPMA观察表明：La0.67Mg0.33Ni3.0合金由LaNi3相和La2Ni7相组成。然而La0.67Mg0.33Ni3.0-xAlx（x=0．1，0．2，0．35）合金不含LaNi3相。研究结果表明Al替代Ni改变了La0．67Mg0．33Ni3.0合金的相结构，Al替代Ni不利于La0．67Mg0．33Ni3.0合金中LaNi3相的形成。此外，随Al含量的增加，La0.67Mg0.33Ni3.0-xAlx（x=0．1，0．2，0．35）合金的相结构也发生了变化。WDS分析表明：随La0.67Mg0.33Ni3.0-xAlx合金中X的增加，Al在LaNis相中的含量增加，但Al在LaNi2相的含量很少并且几乎不随X变化。电化学性能测试表明：Al替代Ni提高了La0.67Mg0.33Ni3.0合金电极的循环稳定性。但La0.67Mg0.33Ni3.0-xAlx合金电极的放电容量却随Al含量的增加而明显降低。     

Influences of stoichiometric ratio B/A on structures and electrochemical behaviors of La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x=0-0.6) hydrogen storage alloys

In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of the AB3.5-4.1-type electrode alloys, the La-Mg-Ni-Co system La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x= 0, 0.2, 0.4, 0.6) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The results show that the structures and electrochemical performances of the alloys are closely relevant to the B/A ratio. All the alloys exhibit a multiphase structure, including two major phases, (La, Mg)2Ni7 and LaNi5, and a residual phase LaNi2, and with rising ratio B/A, the (La,Mg)2Ni7 phase decreases and the LaNi5 phase increases significantly. When ratio B/A=3.7, the alloys obtain the maximum discharge capacities. The high rate discharge(HRD) capability of the alloy (M=Ni) monotonously rises with growing B/A ratio, but that of the alloy (M=Co) first mounts up then declines. The cycle stability of the alloy (M=Co) monotonously increases with rising B/A ratio, but it first decreases slightly then increases for the alloy (M=Ni). The discharge potential of the alloy (M=Ni) declines with increasing B/A ratio (x＞0.2), but for the alloy (M=Co), the result is contrary. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed ratio B/A=3.7, the Co substitution enhances the discharge capacity from 365.7 to 401.8 mA-h/g, the capacity retention ratio (S100) after 100 charging-discharging cycles from 50.32% to 53.26% and the HRD from 88.65% to 90.69%.     

Electrochemical Hydrogen Storage Characteristics of the as-Cast and Annealed La0.8-xPrxMg0.2Ni3.35Al0.1Si0.05 (x=0~0.4) Electrode Alloys

采用铸造及退火工艺制备了La0.8-xPrxMg0.2Ni3.35Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4)电极合金。系统研究了Pr的替代对合金的结构与电化学储氢性质的影响,结果表明除少量残余LaNi3相外,铸造及退火合金是由六方Ce2Ni7型(La, Mg)2Ni7相与六方CaCu5型LaNi5相构成的。Pr对La的置换对合金的电化学储氢性质产生明显影响,铸造及退火合金的放电容量和高倍率放电能力随Pr含量的增加先升后降。当Pr含量由0增加至0.4时,铸造及退火合金的100次充放电循环后容积保持率S100从64.96%和72.82%分别增加至77.94%和91.81%     

Zr替代La对快淬态A2B7型电极合金结构及电化学性能的影响

用铸造及快淬工艺制备了A2B7型电极合金,合金的名义成分为La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1 (x = 0, 0.05, 0.1, 0.15, 0.2)。深入研究了Zr替代La对合金微观结构及电化学性能的影响。用XRD、SEM、TEM分析了合金的结构。结果表明,铸态及快淬态合金均具有多相结构,含有两个主相(La,Mg)Ni3和LaNi5以及一个残余相LaNi2。Zr替代La使合金中LaNi5相明显增加,并促进快淬态合金中形成非晶相。电化学测试的结果表明,Zr替代La明显降低合金的放电容量,但显著改善合金的电化学循环稳定性。当Zr含量小于0.1时,合金的放电容量随淬速的增加而先增加后减小,合金的循环稳定性随淬速的增加而单调增加。     

Cycle stability of La0.7Mg0.3Ni2.55-xCo0.45Cux （x=0-0.4） electrode alloys

La0.7Mg0.3Ni2.55-xCo0.45Cux（x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were prepared by casting and rapid quenching. Ni in the alloy was partially substituted by Cu in order to improve the cycle stability of La-Mg-Ni system （PuNi3-type） hydrogen storage alloy. The effects of substituting Ni with Cu on the microstructures and cycle stability of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM show that the substitution of Cu for Ni is favourable for the formation of an amorphous in the as-quenched alloy, and this leads to an obvious refinement of the as-quenched alloy grains and a growth of the lattice constants and cell volumes of the as-cast and quenched alloys. The results obtained by the electrochemical measurement indicate that the cycle stability of the alloys significantly rises with the incremental variety of Cu content. When Cu content changes from 0 to 0.4, the cycle lives of the as-cast and quenched （30 m/s） alloys are enhanced from 72 to 88 cycles and from 100 to 121 cycles, respectively.     

快淬对La-Mg-Ni系A_2B_7型电极合金循环稳定性的影响

用熔体快淬工艺制备了La-Mg-Ni系A2B7型La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1（x=0,0.05,0.1,0.15,0.2）电极合金。用XRD、SEM、TEM分析了铸态及快淬态合金的微观结构,用程控电池测试设备测试了铸态及快淬态合金电极的电化学循环稳定性,研究了快淬工艺对合金结构及电化学循环稳定性的影响,探讨了电极合金的失效机理。结果表明,快淬态合金均具有多相结构,包括两个主相（La,Mg）Ni3及LaNi5和一个残余相LaNi2。快淬处理可以显著改善合金的电化学循环稳定性。导致合金失效的主要原因是电极表面被电解液剧烈腐蚀以及合金电极在电化学循环过程中的粉化。     

Effect of Temperature on Structure and Electrode Properties of LaNi3.8Co0.6Mn0.3M0.3 Hydrogen Storage Alloys

对LaNi3.8Co0.6Mn0.3M0.3 (M=Ni, Al, Cu)储氢合金在238,273,303和323 K温度下的结构和电化学性能进行了一系列的实验研究。A,B,C分别代表LaNi4.1Co0.6Mn0.3（Ni替代）,LaNi3.8Co0.6Mn0.3Al0.3（Al替代）和LaNi3.8Co0.6Mn0.3Cu0.3（Cu替代）3种储氢合金,通过X射线衍射仪分别对样品A,B,C的结构进行了研究,对样品A,B,C合金粉末制成的电极进行了模拟电池测试。结果证实,制备的合金均由具有CaCu5型六方晶格结构的LaNi5相构成。3种合金中,Cu替代的合金电极低温性能得到改善,Al替代的合金电极高温放电能力得到提高。交流阻抗图谱分析表明,B合金电极样品的高温放电能力提高是由于合金电极表面形成的致密氧化膜层减缓了合金腐蚀所致,样品B,C的高倍率性能衰退是由于电极表面的充放转移反应和氢原子扩散速率下降造成的,而样品C的优良低温性能则是合金电极表面高的充放电转移反应速率所致。     

Al替代Mg对La2MgNi7.5Al1.5贮氢合金相结构和电化学性能的影响

采用X射线衍射、电子探针和电化学测试研究了La2Mg1-xAlxNi7.5Co1.5(x=0.0,0.1,0.3,0.5)合金的相结构和电化学性能.XRD结果和EPMA观察表明,少量的Al替代Mg(x=0.1)不改变La2MgNi7.5Co1.5合金的相组成,合金仍然由LaNi3相和αLa2Ni7相组成,然而La2Mg0.9Al0.1Ni7.5Co1.5合金中LaNi3相的丰度明显下降,αLa2Ni7相的丰度则增加,较多的Al替代Mg改变了La2MgNi7.5Co1.5合金的相组成并导致合金中LaNi3相消失,La2Mg1-xAlxNi7.5Co1.5合金中Al含量的变化对合金中不同相晶胞参数的影响不相同.此外,少量的Al替代Mg(x=0.1)几乎不降低La2MgNi7.5Co1.5合金的贮氢容量和最大电化学放电容量,但随La2Mg1-xAlxNi7.5Co1.5合金中Al含量的增加,合金的贮氢容量、最大电化学放电容量和活化性能不断下降,Al替代Mg能明显提高La2MgNi7.5Co1.5合金的电化学循环稳定性,对提高该合金电极的高倍率放电性能也是有利的.     

快淬对La0.7Mg0.3Co0.45Ni2.55-xCux (x=0-0.4)电极合金微观结构及电化学性能的影响

应用铸造及快淬工艺制备了La0 7Mg0.3Co0.45Ni2.55-xCux (x=0, 0.1, 0.2, 0.3, 0.4)贮氢电极合金,研究了快淬工艺对合金微观结构及电化学性能的影响.XRD,SEM及TEM的分析结果表明,铸态及快淬态合金具有多相结构,包括(La,Mg)Ni3相,LaNi5相以及LaNi2相.快淬对合金的相组成没有明显影响,但显著地改变了合金的相丰度.快淬还显著地改善合金的成分均匀性,并使合金的晶粒明显细化.电化学测试的结果表明,快淬大幅度提高合金的电化学循环稳定性,但使合金的放电容量和活化性能下降.快淬对合金的放电电压特性具有明显的影响,当淬速大于15m/s时,快淬降低合金的放电电压,并使放电平台的斜率明显增大.     

快淬对RE-Mg-Ni系A_2B_7型贮氢合金动力学性能的影响(英文)EI北大核心CSCD

合金的电化学贮氢动力学性能是其应用于动力电池的重要因素。为了提高RE-Mg-Ni系A2B7型贮氢合金的动力学性能,用M(M=Pr,Zr)部分替代La,并采用快淬处理制备了La0.65M0.1Mg0.25Ni3.2Co0.2Al0.1(M=Pr,Zr)电极合金。研究了元素替代和快淬处理对合金结构及电化学贮氢动力学性能的影响。XRD及TEM结果显示,铸态及快淬态合金均为多相结构,包含(La,Mg)2Ni7和LaNi5主相以及少量的残余相LaNi2。Pr替代快淬态合金为纳米晶结构,而Zr替代快淬态合金为类非晶结构,说明Zr部分替代La促进了非晶的形成。电化学测试表明合金的高倍率放电性能(HRD)随着快淬速度的增加先增大后减小。此外,电化学阻抗谱(EIS),塔菲尔极化曲线以及电势阶跃测试均表明合金的电化学动力学性能随着快淬速度的增加先增大后减小。     

Cycle stabilities of the La0.7Mg0.3Ni2.55−xCo0.45Mx (M = Fe, Mn, Al; x = 0, 0.1) electrode alloys prepared by casting and rapid quenching

In order to improve the cycle stability of La–Mg–Ni system (PuNi₃-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Fe, Mn and Al, and the electrode alloys La_0.7Mg_0.3Ni_2.55−xCo_0.45M_x (M = Fe, Mn, Al; x = 0, 0.1) were prepared by casting and rapid quenching. The effects of the substitution of Fe, Mn and Al for Ni and rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Mn obviously raises the amount of the LaNi₂ phase. The substitution of Al and Fe leads to a significant refinement of the as-quenched alloy's grains. The substitution of Al strongly restrains the formation of an amorphous in the as-quenched alloy, but the substitution of Fe is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Mn and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive influence of the substitution elements on the cycle stabilities of the as-cast alloys is in proper order Al > Fe > Mn, and for as-quenched alloys, the order is Fe > Al > Mn. Rapid quenching engenders an inappreciable influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.     

A2B7型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La0.75Mg0.25Ni3.5-xMnx(x=0,0.05,0.1,0.15,0.2)四元贮氢合金,系统地研究合金B侧Mn对Ni部分替代对合金相结构及电化学性能的影响。XRD分析表明,La0.75Mg0.25Ni3.5-xMnx由La2Ni7相(包括Gd2Co7型高温相和Ce2Ni7型低温相)组成。此外,Mn的加入,使该类合金中出现LaNi5相,但是在含Mn量较高(x=0.15,0.2)的合金中LaNi5相消失。电化学测试表明,随Mn含量的增加,合金电极活化次数变化不大,合金电极的最大放电容量减小,高倍率放电性能、交换电流密度变差,循环稳定性、极限电流密度均得到明显的改善。