Designing appropriate heat treatment temperature for LaNi3.8Al0.75Mn0.45 alloy

The effect of heat treatment on microstructure, equilibrium hydrogen sorption pressure and plateau slope of LaNi3.8Al0.75Mn0.45 alloy was investigated. X-ray diffraction (XRD) analysis indicates that annealed alloys have single phase and the same hexagonal structure as that of LaNi5 alloy (CaCu5 type, P6/mmm ). The cell parameters of alloys fluctuate with the increasing annealing temperature. The equilibrium hydrogen pressure and plateau slope are a parabola function with annealing temperature for LaNi3.8Al0.75Mn0.45 alloy. By this relationship, an appropriate heat treatment temperature for LaNi3.8Al0.75Mn0.45 alloy is determined to about 1220-1230 K by mathematic simulation process. However, the maximum hydrogen storage capacity of alloys does not affected by the annealing temperature.     

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。     

La0．7Mg0．3Ni3．4-xCo0．6Mnx（x=0．0～0．5）贮氢电极合金的结构、储氢特性及电化学性能

La0．7Mg0．3Ni3．4-xCo0．6Mnx(x=0．0～0．5)合金主要由(La，Mg)Ni3相和LaNi5相构成，各相的晶胞参数和晶胞体积均随Mn含量的增加而增大。随Mn含量的增加，合金的放氢平衡压力从0．128MPa(x=0．0)下降到0．067MPa(x=0．5)，导致最大吸氢量从x=0．0时的1．19％(质量分数，下同)逐渐增加到x=0．4时的1．38％。合金的最大放电容量随Mn含量的增加首先从330．4mAh／g（x=0．0)增加到360．6mAh／g(x=0．4)，然后减小到346．9mAh／g(x=0．5)。随Mn替代量的增加，合金电极的高倍率放电能力先改善后降低，合金电极的表面反应阻抗先降低后升高，而氢的扩散系数先增加后减小，说明合金的电化学动力学性能首先提高然后降低。     

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。     

LaNi4.25Al0.75合金的结构与储氢性能（英文）

采用XRD、吸氢PCT曲线、吸氢动力学曲线、XPS和粒径分析等测试方法,研究LaNi4.25Al0.75合金的结构和储氢性能;推导LaNi4.25Al0.75合金的四晶胞结构,分析LaNi4.25Al0.75合金的结构与性能的内在联系。结果表明:LaNi4.25Al0.75合金具有快速吸氢性能和较好的抗燃烧能力,其吸氢平台压和温度之间的函数关系式为lnpeq=-4820/T+12.46,合金的吸氢速率随着温度的升高而降低。     

Effects of Co Substitution for Ni on Microstructures and Electrochemical Properties of LaNi3.8 Hydrogen Storage Alloys

系统研究了Co替代Ni对LaNi3.8型LaNi3.8-xCox(x=0.0,0.2,0.4,0.6)贮氢合金组织结构和电化学性能的影响。研究表明,所有合金都由LaNi5、Ce5Co19和Pr5Co19相组成。随着Co含量的增加,3个相的相丰度发生变化,而且单胞体积也相应的增加,这使得合金的放氢平台压降低到镍氢电池需要的范围(0.01~0.1 MPa)。与LaNi3.8相比,含Co合金的循环性能得到改善。LaNi3.4Co0.4具有最大的放电容量,这一点与固态放氢量一致。LaNi3.6Co0.2倍率放电性能最好,具有最大的交换电流密度(Io)和最小的电荷转移电阻(Rct)。     

LaNixMn0.26Aly合金的吸放氢性能研究

对LaNixMn0.26Aly合金的储氢性能进行了研究。结果表明,与LaNi4.61Mn0.26Al0.13合金相比,LaNi4.5Mn0.26Al0.13合金的晶格常数和晶胞体积均变大,吸氢平台压力略有降低,放氢平台压力基本不变,滞后因子有所改善,储氢容量略有减少,氢化物生成焓绝对值变大,氢化物稳定性增加;对于LaNi4.4Mn0.26Al0.34合金,Al替代部分Ni使合金的晶格常数和晶胞体积变大,吸放氢平台压力明显降低,滞后因子明显改善,吸氢动力学性能显著提高,氢化物生成焓绝对值变大,氢化物更加稳定,但储氢容量有所减少。     

Structure and electrochemical properties of La-Mg-Ni system hydrogen storage alloys with different Co contents

1 INTRODUCTIONTo increase the discharge capacity of nickel/metal-hydride ( Ni/ MH) batteries , new types ofhydrogen storage alloys with higher energy densityhave been paid considerable attention by research-ers . Particularly , recent investigations on theR-Mg-Ni (R=rare earth or Ca element) systemhydrogen storage alloys have led to a newseries ofternary alloys with a high hydrogen storage capaci-ty[1 3]. Kohno et al[4]found that the maxi mumdis-charge capacity of the La0 .7Mg0 .3Ni2 …     

Effects of substituting Ni with M (M=Cu, Al and Mn) on microstructures and electrochemical characteristics of La-Mg-Ni system (PuNi3-type) electrode alloys

In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Cu, Al, Mn;x =0,0.1) were prepared by casting and rapid quenching. The effects of element substitution and rapid quenching on the microstructures and electrochemical performances of the alloys were investigated. The results by XRD, SEM and TEM show that the alloys havea multiphase structure, including the (La, Mg)Ni3 phase, the LaNi5 phase and the LaNi2 phase. The rapid quenching and element substitution have an imperceptible influence on the phase compositions of the alloys, but both change the phase abundance of the alloys. The rapid quenching significantly improves the composition homogeneity of the alloys and markedly decreases the grain size of the alloys. The Cu substitution promotes the formation of an amorphous phase in the as-quenched alloy, and a reversal result by the Al substitution. The electrochemical measurement indicates that the element substitution decreases the discharge capacity of the alloys, whereas it obviously improves the cycle stability of the alloys. The positive influence of element substitution on the cycle life of the alloys is in sequence Al＞Cu＞Mn, and negative influence on the discharge capacity is in sequence Al＞Mn＞Cu. The rapid quenching significantly enhances the cycle stability of the alloys, but it leads to a different extent decrease of thedischarge capacity of the alloys.     

Investigation Of Stability And Hydrogen Storage Properties Of LaNi5-XMx（M=Al, Mn) Alloys

通过对LaNi5-xAlx和LaNi5-xMnx两个合金系的晶胞参数、热力学性能、吸氢量、平衡氢压等储氢性能进行对比和分析，建立了LaNi5-xMx(M=Al，Mn)合金系中的x与平台压力以及温度间的对应关系，探讨了晶格常数和晶胞体积及合金稳定性的变化对合金系储氢性能的影响．结果表明，与LaNi5-xAlx相比较，LaNi5-xMnx合金的晶胞体积较大，使其平衡氢压降得更低；随x的增加，LaNi5-xMnx合金晶胞体积膨胀的各向异性程度(即晶轴比变化)较小，且合金稳定性的变化较小，随z增加吸氢量衰减不明显．     

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%.     

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。     

TiV0.8-xCr1.2Alx合金的结构与贮氢性能

研究了Al对TiV0.8-xCr1.2Alx(x=0、0.05、0.1、0.15、0.2)合金的结构与贮氢性能的影响.XRD、PCT等测试研究表明:TiV0.8-xCr1.2Alx合金均为单相bcc结构,铸态时主相为树枝状晶组织;随着Al含量由0增加到6.67 at%,合金的晶格常数变大,吸氢量和放氢量减小,氢化物标准生成焓变与生成熵变增大.放氢的平台压随着Al含量的增加而线性增大.TiV0.75Cr1.2Al0.05合金最大吸氢量达3.887%(质量分数),有效吸氢量达2.288%.     

Effect of Ni on Mg based hydrogen storage alloy Mg3Nd

Magnesium-neodymium based alloys were prepared by induction melting in an alumina crucible under protection of pure argon atmosphere. XRD patterns show that the as-melted Mg-Nd and Mg3NdNi 0.1 diffraction peaks can be excellently indexed with D03 structure (BiF3 type, space group Fm3m ). The lattice constant of Mg3Nd phase is 0.7390 nm, which is determined by XRD analysis using Cohen's extrapolation method. The reversible hydrogen storage capacity reaches 1.95wt.% for Mg3Nd and 2.68wt.% for Mg3NdNi0.1 . The desorption of hydrogen takes place at 291 ℃ for Mg3Nd and at 250 ℃ for Mg3NdNi 0.1 . The alloys could absorb hydrogen at room temperature with rapid hydriding and dehydriding kinetics after only one cycle. The enthalpy (ΔH ) and entropy (ΔS ) of Mg3Nd-H dehydriding reaction were -68.2 kJ·mol-1 H2 and -0.121 kJ·(K·mol)-1 H2 determined by using van't Hoff plot according to the pressure-composition-isotherms (P-C-I) curve measured at different temperatures. Hydrogen absorption kinetic property of Mg3NdNi 0.1 alloy was also measured at room temperature.     

Effects of La substitution on microstructure and hydrogen storage properties of Ti–Fe–Mn-based alloy prepared through melt spinning

The as-spun Ti_1–xLa_xFe_0.8Mn_0.2 (x=0, 0.01, 0.03, 0.06, 0.09, molar fraction) alloys were prepared by melt spinning. The effects of La substitution for Ti on the microstructure, hydrogen storage kinetics and thermodynamics of TiFe-type Ti–Fe–Mn-based alloy were investigated. The as-spun alloys hold the TiFe single phase, which transforms to TiFeH_0.06, TiFeH, and TiFeH₂ hydrides after hydrogenation. La substitution promotes the formation of micro-defects (such as dislocations and grain boundaries) in the alloys, thus facilitating hydrogen diffusion. In addition, the hydrogen storage kinetics properties are improved after introducing La element. With the rise of La content, the hydrogen storage capacity decreases firstly and then increases, but the absolute value of hydriding enthalpy change (|ΔH|) increases firstly and then reduces. When x=0.01, the maximum value of |ΔH| is obtained to be (25.23±0.50) kJ/mol for hydriding, and the alloy has the maximum hydrogen absorption capacity of (1.80±0.04) wt.% under the conditions of 323 K and 3 MPa.     

Ti0.9Zr0.2Mn（1.8—x）MxV0.2（M=Ni,Cr;x=0,0.2）合金的贮氢性能

研究了Ti0.9Zr0.2Mn(1.8-x)MxV0.2(M=Ni,Cr;x=0,0.2)合金的晶体结构与贮氢性能。结果表明,Ti0.9Zr0.2Mn1.6Ni0.2V0.2和Ti0.9Zr0.2Mn1.6Cr0.2V0.2的贮氢量达到240mL/g。合金的主相均为C14 Laves相,镍,铬的取代使点阵常数和晶胞体积增大,P－C－T曲线的滞后降低,压力平台的倾斜度增加。     

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。     

Effect of vanadium content on hydrogen storage property in Ti-V-Cr alloys

The effect of vanadium content on the microstructure and hydrogen absorption/desorption properties in Ti-V-Cr alloys was studied. The results show that with the increase of vanadium content from 5at.%, 10at.% to 35at.%, the hydrogen absorption capacity increases gradually from 1.14wt.%, 1.57wt.% tO2.84wt.%, and the hydrogen desorption capacity also increase from 0.43, 0.64, to 1.59. This indicates that the alloy with 35at.% vanadium content has the most optimum hydrogen storage capacity among these alloys. The microstructure observation also indicates that the alloy with 35at.% vanadium turns to be the single-phase alloy of the BCC solid solution. Furthermore, with the increase of vanadium content the pressure plateau becomes more distinguishing and shifts to lower pressure level gradually. The kinetics of hydrogen absorption was also found to be dependent with the vanadium content in these discussed alloys.     

La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-xFex合金的相结构和电化学储氢性能（英文）

采用感应熔炼和热处理的方法制备La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75?xFex(x=0~0.20)合金,并研究合金的相结构和电化学储氢性能。全部合金均为单一的具有CaCu5结构的LaNi5相,LaNi5相的晶格常数a和晶胞体积随着x值的增加而增大。最大放电容量随着x值的增加从319.0mA·h/g(x=0)降低到291.9mA·h/g(x=0.20)。在1200mA/g的电流密度下HRD值从53.1%(x=0)降低到44.2%(x=0.20)。合金电极的循环稳定性随着x值的增加而增强,这主要归因于合金抗粉化能力的增强。     

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。