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%。     

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。     

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。     

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.     

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%     

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。     

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。     

Structure and electrochemical properties of low-cobalt La1- xLixNi3.2Co0.3Al0.3(0≤x≤0.2) hydrogen storage electrode alloys

The structure and electrochemical properties of a new low cobalt hydrogen storage electrode alloys La1-xLixNi3.2Co0.3Al0.3(0≤ x ≤0.2) were investigated with a different additions of Li in replacement of La. With the increase of Li contents the maximum discharge capacity increases from 240 mAh·g -1 ( x =0) to 328.4 mAh·g -1(x=0.1) and the cycle stability is improved correspondingly. The capacity decay can remaiN28.6% ( x =0.2) after 230 charge/discharge cycles. The high rate discharge(HRD) ability of the alloys( x≤0.1) is improved and the best HRD is 34.1%( x =0.1) under the discharge current density 1200 mA·g -1 . It is found that the prepared alloys are basically composed of LaNi5 as matrix phase and LaNi3 as second phase( x ≤0.1). But the abundance of LaNi3 phase dramatically decreases with increasing x . When x =0.2, a new phase Al(NiCo)3 is formed.     

A2B7型La0.75Mg0.25Ni3．5-xAlx（x=0-0．3）合金相结构及电化学性能

采用感应熔炼方法制备了A2B7型La0.75Mg0.25Ni3．5-xAlx（x=0，0．02，0．06 0.1，0．3）四元贮氢合金，系统研究了Al元素部分替代Ni对A2B7型La0.75Mg0.25Ni3．5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由单一La2Ni7相组成：Al元素加入后，开始出现CaCu5型LaNi5相，当x=0．3时，LaNis相成为合金的主相。Rietveld分析表明：随着Al含量的增加，LaNi5相逐渐增多，Al的加入利于CaCu5型LaNi5相的形成。电化学测试表明：Al替代Ni对A2B7型合金La0.75Mg0.25Ni3．5电极活化性能影响不大：而最大放电容量随Al在La0.75Mg0.25Ni3．5-xAlx，合金中替代量的增加而减小。当放电电流密度为1600mA／g时，合金的倍率放电性能由68.8％（x=0）增加到81．16％（x=0．1）然后减小到65．67％（x=0.3）。此外，La0.75Mg0.25Ni3．5-xAlx合金电极循环稳定性先增加而后下降。x=0．06时合金电极容量保持率最大（S100=85.21．％）。     

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。     

纳米晶和非晶Mg20-xLaxNi10(x=0-6)贮氢合金的贮氢行为

用快淬技术制备了Mg2Ni型贮氢合金,合金的名义成分为Mg20-xLaxNi10 (x = 0, 2, 4, 6)。用XRD、SEM、HRTEM分析了合金的微观结构。发现不含La的快淬合金中没有非晶相,但含La快淬合金中显示以非晶相为主。当La含量x≤2时,铸态合金的主相为Mg2Ni相,但随着La含量的进一步增加,铸态合金的主相改变为(La,Mg)Ni3+LaMg3相。应用Sieverts设备研究了铸态及快淬态合金的吸放氢量及动力学,结果表明,x=2的合金吸放氢量及动力学随淬速的增加而增加,但对于x=6的合金,结果是相反的。电化学测试结果表明,x=2合金的放电容量随淬速的增加而增加,而对于x=6合金,结果也是相反的。快淬显著地提高了x=2, 6合金的循环稳定性     

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.     

La(1-x)MgxNi4.25Al0.75(x=0-0.3)合金的结构与储氢性能研究

采用三步感应熔炼法制备了La(1-x)MgxNi4.25Al0.75 (x=0.0,0.1,0.2,0.3) 储氢合金,对该系列合金的晶体结构和储氢性能方面进行了研究。晶体结构和相分析结果表明,当x=0.0和0.1时,合金由单一的LaNi4Al相组成;而x=0.2和0.3时,合金由LaNi4Al相, (La,Mg)Ni3相和AlNi3相构成。随着Mg含量x从0.2增至0.3时,合金的第二相丰度和吸/放氢平衡压明显升高,同时储氢容量减小。研究发现,当Mg添加量x=0.1时,合金除具有良好的储氢容量和低平台压外,其吸氢动力学性能更好。     

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…     

添加Si对A_2B_7型电极合金结构及电化学贮氢性能的影响(英文)

为改善La–Mg–Ni系A2B7型合金的电化学贮氢性能,在合金中添加一定量的Si元素,通过真空熔炼及退火处理的方法制备La0.8Mg0.2Ni3.3Co0.2Six(x=0-0.2)电极合金。研究Si元素的添加对合金结构及电化学贮氢性能的影响。结果表明,铸态及退火态合金均为多相结构,分别为Ce2Ni7型的(La,Mg)2Ni7相和CaCu5型的LaNi5相以及少量的残余相LaNi3。Si元素的添加没有改变合金的主相,但使得合金中的(La,Mg)2Ni7相减少而LaNi5相增加。添加Si显著地影响了合金的电化学性能。随着Si含量的增加,铸态及退火态合金的放电容量逐步降低,但循环稳定性却随着Si含量的增加而增强。此外,合金电极的高倍率放电性能、极限电流密度、氢扩散系数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Si含量的增加先增加而后减小。     

La1＋xMg2-xNi9（x=0，0．5，1．0，1．5）合金的储氢性能及电化学性能研究

利用高频熔炼方法制备了La1＋xMg2-xNi9（x=0，0．5，1．0，1．5）系列合金，并对其进行了XRD分析和储氢容量及电化学性能测定。结果表明：随着La含量增大，合金中LaNi5和（La，Mg）Ni3相转变为LaNi3相，且Mg2Ni相出现，晶胞体积也增大，合金的储氢容量和电化学性能提高；当x=1．5时，Mg2Ni相消失，合金的储氢性能有所下降。当x=1．0时，即La2MgNi9合金具有较好的储氢容量及电化学容量。     

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 La0.75-xMxMg0.25Ni3.2Co0.2Al0.1 (M =Zr, Pr; x =0, 0.1) alloys prepared by melt spinning

In order to ameliorate the electrochemical hydrogen storage performances of La-Mg Ni system A2B7-type electrode alloys,the partial substitution ofM (M =Zr,Pr) for La was performed.The melt spinning technology was used to fabricate the La0.75-xMxMg0.25Ni3.2Co0.2Al0.1 (M =Zr,Pr; x =0,0.1) electrode alloys.The influences of the melt spinning and substituting La with M (M =Zr,Pr) on the structures and the electrochemical hydrogen storage characteristics of the alloys were investigated.The analysis of XRD,SEM,and TEM reveals that the as-cast and spun alloys have a multiphase structure composed of two main phases (La,Mg)2Ni7 and LaNi5 as well as a residual phase LaNi2.The as-spun (M =Pr) alloy displays an entire nanocrystalline structure,while an amorphous-like structure is detected in the as-spun (M =Zr) alloy,implying that the substitution of Zr for La facilitates the amorphous formation.The electrochemical measurements exhibit that the substitution of Pr for La clearly increases the discharge capacity of the alloys; however,the Zr substitution brings on an adverse impact.Meanwhile,the M (M =Zr,Pr) substitution significantly enhances its cycle stability.The melt spinning exerts an evident effect on the electrochemical performances of the alloys,whose discharge capacity and high rate discharge ability (HRD) first mount up and then fall with the growing spinning rate,whereas their cycle stabilities monotonously augment as the spinning rate increases.     

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。