Enhanced Electrochemical Hydrogen Storage Characteristics of Nanocrystalline and Amorphous Mg20Ni10-xCox (x=0-4) Alloys by Melt Spinning

In order to improve the electrochemical hydrogen storage performances of the Mg2Ni-type alloys, Ni in the alloy was partially substituted by element Co. The nanocrystalline and amorphous Mg20Ni10-xCox (x=0, 1, 2, 3, 4) alloys were prepared by melt-spinning technology. The structures of the as-cast and spun alloys were studied by XRD, SEM and HRTEM. The electrochemical hydrogen storage characteristics of the alloys were measured. The results show that the substitution of Co for Ni leads to the formation of secondary phase MgCo2 without altering the major phase of Mg2Ni. No amorphous phase is detected in the as-spun alloy (x=0), whereas the as-spun alloy (x=4) holds a nanocrystalline and amorphous structure, confirming that the substitution of Co for Ni significantly increases the glass forming ability of the Mg2Ni-type alloy. The substitution of Co for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, including the discharge capacity and the cycle stability, for which the increased glass forming ability by Co substitution is mainly responsible     

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。     

Investigation on Gaseous and Electrochemical Hydrogen Storage Kinetics of As-Quenched Nanocrystalline Mg2Ni-type Alloys

为了改善Mg2Ni型合金气态及电化学贮氢动力学性能,用Cu部分替代合金中的Ni,用快淬技术制备Mg2Ni1-xCux(x=0,0.1,0.2,0.3,0.4)合金,用XRD、SEM、HRTEM分析铸态及快淬态合金的微观结构;用自动控制的Sieverts设备测试合金的气态贮氢动力学性能,用程控电池测试仪测试合金的电化学贮氢动力学.结果表明,所有快淬态合金均具有纳米晶结构,无非晶相形成.Cu替代Ni不改变合金的主相Mg2Ni,但使合金的晶粒显著细化.快淬处理及Cu替代均显著地提高合金的气态及电化学贮氢动力学性能.当淬速从0m/s(铸态被定义为淬速0 m/s)增加到30 m/s时,Mg2Ni0.8Cu0.3合金在5 min内的吸氢饱和率从57.2％增加到92.87％,20 min的放氢率从21.6％增加到49.6％,高倍率放电能力(HRD)从40.6％增加到73.1％,氢扩散系数(D)从1.02×10-11 cm2/s增加到4.08×10 -11 cm2/s,极限电流密度(IL)从113.0 mA/g增加到715.3 mA/g.     

Gaseous and electrochemical hydrogen storage behaviors of nanocrystalline and amorphous Nd-added Mg_2Ni-type alloys

Melt spinning technology was used to prepare the Mg2Ni-type(Mg24Ni10Cu2)100-xNdx(x = 0, 5, 10, 15,20) alloys in order to obtain a nanocrystalline and amorphous structure.The effects of the spinning rate on the structures and gaseous and electrochemical hydrogen storage behaviors of the alloys were investigated.The analysis of X-ray diffraction(XRD), transmission electron microscope(TEM), and scanning electron microscope(SEM) linked with energy-dispersive spectroscopy(EDS)reveals that all the as-cast alloys hold a multiphase structure, involving the main phase Mg2 Ni and some secondary phases such as Mg6 Ni, Nd5Mg41, and Nd Ni.The as-spun Nd-free alloy displays an entire nanocrystalline structure,whereas the as-spun Nd-added alloys hold a nanocrystalline and amorphous structure, and the amorphization degree visibly increases with the spinning rate increasing.The melt spinning ameliorates the hydrogen storage performances of the alloys dramatically.When the spinning rate rises from 0(the as-cast was defined as the spinning rate of 0 m s-1) to 40 m s-1, the discharge capacity increases from 86.4 to 452.8 m Ah g-1, the S20(the capacity maintain rate at 20 th cycle) value increases from53.2 % to 89.7 %, the hydrogen absorption saturation ratio(Ra5, a ratio of the hydrogen absorption quantity in 5 min to the saturated hydrogen absorption capacity) increases from36.9 % to 91.5 %, and the hydrogen desorption ratio(Rd10,a ratio of the hydrogen desorption quantity in 10 min to the saturated hydrogen absorption capacity) increases from16.4 % to 47.7 % for the(x = 10) alloy, respectively.     

La替代Mg对Mg2Ni型合金电化学贮氢性能的影响

用快淬工艺制备了纳米晶和非晶Mg2Ni型Mg2 -xLaxNi (x=0,0.2,0.4,0.6)贮氢电极合金,获得长度连续,厚度约为30μm,宽度约为25 mm的薄带.用XRD、SEM和HRTEM分析了快淬合金薄带的微观结构,测试了合金薄带的电化学性能及电化学交流阻抗谱(EIS).快淬无La合金具有典型的纳米晶结构,...     

Effects of Rapid Quenching on Structure and Hydrogen Storage Characteristics of Mg20Ni10-xMnx (x=0-4) Alloys

为了改善Mg2Ni型合金的贮氢性能,用Mn部分替代合金中的Ni,并采用快淬工艺制备Mg20Ni10-xMnx(x=0, 1, 2, 3, 4)合金。用XRD和HRTEM分析了铸态及快淬合金的微观结构,用自动控制Sieverts设备测试合金的吸放氢动力学,并采用程控电池测试仪测试合金的电化学性能。结果表明,当淬速为20 m/s时,快淬(x=4)合金中出现非晶相,且非晶化程度随淬速的增加而增加。合金的吸放氢量及动力学性能随淬速的增加而增加。此外,快淬显著地改善了合金的电化学性能,包括放电容量及含Mn合金的循环稳定性。     

Nd含量对快淬纳米晶和非晶（Mg24Ni10Cu2）100-xNdx（x=0~20）合金电化学性能的影响

采用快淬技术制备Mg2Ni型纳米晶和非晶（Mg24Ni10Cu2）100-xNdx （x=0,5,10,15,20）合金,研究快淬速度对合金相结构和电化学性能的影响。结果表明,快淬态无 Nd 合金为纳米晶结构,而添加 Nd 元素的快淬态合金为纳米晶和非晶结构,表明添加Nd元素可促进Mg2Ni型合金的非晶形成能力。当快淬速度从0增加至40 m/s时, x=0合金的放电容量从42.5增加至100.6 mA·h/g;x=10合金的放电容量从86.4增加至452.8 mA·h/g。与此同时, x=0合金的循环稳定性（S20）也由40.2%增加到41.1%,而x=10合金的S20值由53.2%增加到89.7%。     

快淬纳米晶和非晶Mg_(20)Ni_(10-x)Co_x(x=0～4)合金的贮氢性能(英文)EI北大核心CSCD

为了改善Mg2Ni型合金的贮氢性能,采用Co部分替代合金中的Ni以及快淬工艺制备了纳米晶和非晶态Mg20Ni10-xCox(x=0,1,2,3,4)贮氢合金。用XRD、SEM、HRTEM分析了铸态及快淬态合金的微观结构,并测试了合金的气态吸/放氢动力学及电化学贮氢性能。结果表明,在快淬无Co合金中没有形成非晶相,但快淬含Co合金中形成一定量的非晶相。Co替代Ni及快淬处理显著地改善了合金的气态吸放氢性能。同时,Co替代Ni也显著地提高了快淬态合金的放电容量和电化学循环稳定性。     

Mg17Al12基储氢合金的表面复相改性

采用机械球磨法制备Mg17Al12合金,系统研究了球磨时间对Mg17Al12形成过程的影响;并以球磨12 h的Mg17Al12合金为基体,添加5%、10%（质量分数）的Ni、Cu单质,通过机械球磨对合金进行表面复相改性。采用P-C-T测试仪测定合金的储氢性能,研究添加不同质量分数的单质对Mg17Al12合金储氢性能的影响。结果表明：球磨12 h Mg17Al12的吸氢速率较慢,吸氢时间较长,需在1400 min达到最大吸氢量为4.1%（质量分数）,接近其理论吸氢量4.4%,Mg17Al12的吸放氢过程是可逆的。Cu对Mg17Al12进行表面复相改性,可以显著改善其吸氢动力学性能,添加5%Cu和10%Cu的合金在623 K,240 min的吸氢量分别为4.07%和3.9%。经过Cu和Ni复相改性后的Mg17Al12具有较好的放氢性能,添加5%Cu合金在553 K放出3%的氢气。Ni对Mg17Al12进行表面复相改性,对其性能有一定的提高,但是和Cu相比,并不明显     

Investigation of Electrochemical Hydrogen Storage Kinetics of Melt Spun Nanocrystalline and Amorphous Mg2Ni-type Alloy

用快淬工艺制备了Mg2Ni型合金,其名义成分为Mg2Ni1-xCox(x=0,0.1,0.2,0.3,0.4)。以XRD、SEM、TEM分析了铸态及快淬合金的结构。用程控模拟电池测试仪测试了合金的电化学贮氢动力学。用电位跃迁法计算了氢在合金中的扩散系数。用电化学工作站测试了合金的电化学交流阻抗谱(EIS)和Tafel极化曲线。结果表明,快淬态无Co合金具有典型的纳米晶结构,而Co含量为0.4的快淬态合金具有纳米晶/非晶结构,表明Co替代Ni可以提高Mg2Ni型合金的非晶形成能力,且快淬态合金的非晶化程度随Co替代量的增加而增加。Co替代Ni显著地提高了合金电化学贮氢动力学。当Co含量从0增加到0.4时,淬速为25m/s的快淬态合金的高倍率放电能力(HRD)从65.3%增加到75.3%,氢扩撒系数(D)从2.22cm2/s增加到3.34cm2/s,极限电流密度(IL)从247.8mA/g增加到712.4mA/g。     

放电等离子烧结技术制备La0．7Mg0．3Ni2．5Cox贮氢合金性能研究

用放电等离子烧结技术（SPS）制备La0．7Mg0．3Ni2．5Cox（x=O．1,0．2,0．3,0．4,0．5）贮氢合金。采用X射线衍射、三电极测试体系和交流阻抗法研究了合金的相结构、贮氢性能和电化学性能。结果表明：合金为多相结构,主相为（La,Mg）2Ni,和（La．Mg）Ni3相;该系列贮氢合金的贮氢容量随x值的增大先增后减,在x=0．4时贮氢容量达1．37％。最大放电容量为365．4mAh／g。合金的活化性能好（活化次数均为1次）,随着x值的增加,贮氢合金的放氢平台压力升高,合金电极表面电荷转移速率增大。     

Electrochemical hydriding performance of Mg–TM–Mm (TM=transition metals,Mm=mischmetal) alloys for hydrogen storage

Eighteen as-cast binary Mg–Ni, Mg–Mm and ternary Mg–Ni–Mm and Mg–Ni–TM (TM=transition metals (Cu, Zn, Mn and Co); Mm = mischmetal containing Ce, La, Nd and Pr) alloys were hydrided by an electrochemical process to determine the alloys with the most potential for electrochemical hydrogen storage. The alloys were hydrided in a 6 mol/L KOH solution at 80 °C for 480 min and at 100 A/m². To assess the electrochemical hydriding performance of alloys, maximum hydrogen concentrations, hydrogen penetration depths and total mass of absorbed hydrogen in the alloys were measured by glow discharge spectrometry. In addition, the structures and phase compositions of the alloys both before and after hydriding were studied by optical and scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction. It was determined that the highest total amount of hydrogen was absorbed by the Mg–25Ni–12Mm and Mg–26Ni (mass fraction, %) alloys. The maximum hydrogen concentrations in the Mg–25Ni–12Mm and Mg–26Ni alloys were 1.0% and 1.6%, respectively. The main hydriding product was the binary MgH₂ hydride, and the ternary Mg₂NiH₄ hydride was also detected in the Mg–25Ni–12Mm alloy. The electrochemical hydriding parameters achieved are discussed in relation to the structures of alloys, alloying elements and hydriding mechanisms.     

Enhanced Hydriding and Dehydriding Kinetics of as-Spun Nanocrystalline Mg2Ni-Type Alloy Substituting Ni with Cu

为了改善Mg2Ni型合金的吸放氢动力学性能,用Cu部分替代合金中的Ni。用快淬工艺制备了纳米晶Mg2Ni1-xCux(x=0,0.1,0.2,0.3,0.4)贮氢合金,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设备测试了合金的吸放氢动力学性能。结果表明,快淬态合金具有纳米晶结构,Cu替代Ni不改变合金的主相Mg2Ni,但导致形成第二相Mg2Cu。随Cu含量的增加,合金的吸氢量先增加而后减小,但合金的放氢量随Cu含量的增加而单调增加。快淬显著提高合金的吸放氢量并改善合金的吸放氢动力学。     

Influence of rapid quenching on hydrogen storage characteristics of nanocrystalline Mg2Ni-type alloys

Nanocrystalline Mg2Ni-type alloys with nominal compositions of Mg20Ni10–xCux(x=0,1,2,3,4,mass fraction,%) were synthesized by rapid quenching technique.The microstructures of the as-cast and quenched alloys were characterized by XRD,SEM and HRTEM.The electrochemical hydrogen storage performances were tested by an automatic galvanostatic system.The hydriding and dehydriding kinetics of the alloys were measured using an automatically controlled Sieverts apparatus.The results show that all the as-quenched alloys hold the typical nanocrystalline structure and the rapid quenching does not change the major phase Mg2Ni.The rapid quenching significantly improves the electrochemical hydrogen storage capacity of the alloys,whereas it slightly impairs the cycling stability of the alloys.Additionally,the hydrogen absorption and desorption capacities of the alloys significantly increase with rising quenching rate.     

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。     

Effects of chemical coating with Ni on electrochemical properties of Mg2Ni hydrogen storage alloys

The effects of nickel coating on the electrochemical properties of Mg2Ni hydrogen storage alloys are presented in this paper. X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques were employed to examine the crystal structure and surface morphologies of the bare and Ni-coated Mg2Ni alloys. The electrochemical properties of alloys were characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that Ni coating not only decreased the charge transfer resistance, but also decreased the H atom diflusion resistance for Mg2Ni alloys. It was also found that Ni coating effectively improved the discharge capacity, but decreased the cycling performance of the as-synthesized Ni-coated Mg2Ni alloys. The discharge current has a great impact on the cycling performance of the as-synthesized Ni-coated Mg2Ni alloys.     

退火热处理对Nd0.75Mg0.25(Ni0.8Co0.2)3.5储氢合金结构和性能的影响

采用中频感应熔炼制备Nd0.75Mg0.25(Ni0.8Co0.2)3.5储氢合金,在0.03 MPa氩气氛围进行退火,退火温度分别为850,900和950 ℃,保温时间均为7 h。分别对合金的电化学性能、气态储氢性能和合金的微观结构进行研究。结果表明,合金在退火热处理前后的相组成没有发生明显变化,主相均为Ce2Ni7型(Nd,Mg)2(Ni,Co)7相和CaCu5型NdNi5相。合金中晶粒尺寸随着退火温度的升高而增大,相界面则减少,退火消除晶格应力、增加成分均匀性、增加储氢容量;同时有部分Mg在热处理过程中损失导致储氢容量的下降。900 ℃热处理使得Nd0.75Mg0.25(Ni0.8Co0.2)3.5合金表现出较好的储氢性能,最大电化学放电容量为359 mAh/g,合金电极在100次循环后容量保持率为90.3%,气态储氢容量达到1.65%（质量分数,下同）。     

Si元素的添加对La-Mg-Ni系合金贮氢性能的影响

为了提高La-Mg-Ni系A2B7型贮氢合金的电化学循环稳定性,添加少量Si,用铸造工艺制备了La0.75Mg0.25Ni3.3Co0 2Six(x=0,0.05,0.1,0.15,0.2)贮氢合金,分析并测试了其微观结构、电化学性能以及氢扩散系数.结果表明,合金具有多相结构,主相由CaCu5型相和Ce2Ni7型相组成...     

球磨Mg50Ni50＋x wt%Ti（x=0,1,3,5）合金的贮氢性能

为了改善镁基贮氢合金的贮氢性能,在合金中加入不同量的Ti作为催化剂,用机械球磨法制备出Mg50Ni50＋x wt%Ti（x=0,1,3,5）合金粉末。用XRD、SEM分析了合金的微观结构,研究了Ti含量的变化对合金气态吸氢动力学及电化学性能的影响。结果表明：随着Ti含量的增加,合金相中出现了TiNi2相,TiNi2相不利于气态吸氢及电化学贮氢性能,但对合金的容量保持率及高倍率放电性能有很好的促进作用。     

钕含量对Mg-Cu-Nd非晶合金贮氢性能的影响

通过溶体快淬成功制备了（Mg65Cu25）100-xNdx（x=2，5，7，10）非晶／纳米晶贮氢合金，利用透射电镜、x射线衍射仪和差热分析仪研究了合金的微观组织结构及其热性能，采用ARBINBTW-2000型电池测试仪研究了合金的贮氢性能。结果表明：随着钕含量的增高，合金的贮氢量呈现上升趋势。非晶（Mg65Cu25）93Nd7合金具有最好的贮氢动力学性能和贮氢容量，最高贮氢量达到3．O％（质量分数），而纳米晶（Mg65Cu25）98Nd2具有最低的贮氢动力学性能和贮氢容量。研究还表明，随着钕含量的增高，合金的非晶形成能力增强，非晶的这种独特的短程有序结构是提高贮氢性能的主要因素。