Electrochemical properties of TiV-based hydrogen storage alloys

The electrochemical properties of the super-stoichiometric TiV-based hydrogen storage electrode alloys(Ti0.8Zr0.2)(V0.533Mn0.107Cr0.16Ni0.2)x(x=2,3,4,5,6)were studied.It is found by XRD analysis that all the alloys mainly consist of a C14 Laves phase with hexagonal structure and a V-based solid solution phase with BCC structure.The lattice parameters and the unit cell volumes of the two phases decrease with increasing x.The cycle life.the linear polarization.the anode polarization and the electrochemical impedance spectra of the alloy electrodes were investigated systematically.The overall electrochemical properties of the alloy electrode are found improved greatly as the result of super-stoicfhiometry and get to the best when x=5.     

Tix(AlNbZr)100-x系多主元合金力学性能的第一性原理研究

通过对合金的固溶体参数以及相比例图进行计算,研究了Ti_x(AlNbZr)_100-x系多主元合金的固溶体相形成规律,运用基于密度泛函理论的第一性原理方法研究了Ti含量变化对Ti_x(AlNbZr)_100-x系多主元合金结构稳定性以及力学性能的影响。结果表明,Ti_x(AlNbZr)_100-x系多主元合金可以形成稳定的固溶体相,且合金主要由BCC相和Al₃Zr₅相组成,随Ti含量增加,合金的液相线降低,Al₃Zr₅相的相形成温度减小,直到Ti含量为60%~70%时,Al₃Zr₅相消失,合金由单一BCC相组成;Ti含量增加可以提高合金的结构稳定性,当Ti含量为25%~70%时,合金具有良好的力学稳定性,合金的体积模量、剪切模量以及杨氏模量随着Ti含量的增加呈上升趋势。Ti_x(AlNbZr)_100-x系多主元合金的基态能量和形成热随着Ti含量的增加而降低,表明增加Ti含量可以增加该合金系的热力学稳定性,使合金更易形成固溶体相。     

Microstructure Characterization and Fracture Toughness of Laves Phase-Based Cr–Nb–Ti Alloys

Three Laves phase-based alloys with nominal compositions of Cr2Nb–x Ti(x = 20,30,40,in at%) have been prepared through vacuum non-consumable arc melting.The results show that the microstructures of Cr2Nb-(20,30) Ti alloys are composed of the primary Laves phase C15–Cr2(Nb,Ti) and bcc solid solution phase,while the microstructure of Cr2Nb–40Ti alloy is developed with the eutectic phases C15–Cr2(Nb,Ti)/bcc solid solution.The measured fracture toughness of ternary Laves phase C15–Cr2(Nb,Ti) is about 3.0 MPa m1/2,much larger than 1.4 MPa m1/2for binary Laves phase Cr2 Nb.Meanwhile,the fracture toughness of Cr2Nb–x Ti(x = 20,30,40) alloys increases with increasing Ti content and reaches 10.6 MPa m1/2in Cr2Nb–40Ti alloy.The eutectic microstructure and addition of Ti in Cr2 Nb are found to be effective in toughening Laves phase-based alloys.     

快速凝固钛钒系贮氢合金电化学性能研究

研究了快速凝固处理对钛钒系贮氢电极合金Ti0.8Zr0．2V2．4Mn0．48Cr0．72Ni0．9的相结构、特别是电化学性能的影响规律。XRD研究表明：合金主要由六方结构的C14 Laves相和体心立方结构的钒基固溶体相所组成，快速凝固减少了合金中C14 Laves相的含量。电化学性能分析表明：快速凝固降低了合金电极的最大放电容量，增加了电极的活化次数，提高了电极表面的反应阻抗，恶化了电极的动力学性能，但是却大大改善了合金电极的循环稳定性。     

Microstructure and Mechanical Properties of a Refractory CoCrMoNbTi High-Entropy Alloy

In this work, a new refractory high-entropy alloy, the Co-Cr-Mo-Nb-Ti system, was proposed as a family of candidate materials for high-temperature structural applications. CoCrMoNbTi _x (x values in terms of molar ratios, x = 0, 0.2, 0.4, 0.5 and 1.0) alloys were prepared by vacuum arc melting. The effects of variations in the Ti content on the phase constituents, microstructure and mechanical properties of the alloys were investigated using x-ray diffractometry, scanning electron microscopy equipped with energy-dispersive x-ray spectroscopy and compressive testing. The results showed that the CoCrMoNbTi_0.4 alloy possessed a typical cast dendritic microstructure consisting of a single body-centered cubic (BCC) solid solution. Laves phases (Cr₂Nb and Co₂Ti) were formed in other alloys with different Ti contents. The results were discussed in terms of the mixing enthalpy, atomic size difference, electronegativity difference and valance electron concentrations among the elements within alloys. The alloy hardness exhibited a slightly decreasing trend as the Ti content increased, resulting from the coarser microstructure and reduced amount of Laves phases. Augmented Ti content increased the compressive strength, but decreased the ductility. Particularly, for the CoCrMoNbTi_0.2 alloy, the hardness, compressive strength and fracture strain were as high as 916.46 HV_0.5, 1906 MPa and 5.07%, respectively. The solid solution strengthening of the BCC matrix and the formation of hard Laves phases were two main factors contributing to alloy strengthening.     

合金化对ZrMn2基Laves相贮氢合金相组成的影响

研究了Ni、V、Cr、Co、Fe、Cu和Ti等合金化元素取代ZrMn2 基Laves相贮氢合金的B侧或A侧对合金相组成的影响。结果表明 ,采用不同的元素对A侧或B侧进行部分取代 ,将引起ZrMn2 基合金相组成的变化。采用Ni取代Mn后 ,ZrMn2 合金的主相结构转变为C15型Laves相 ,表明Ni为C15相稳定元素。对Zr Mn Ni三元合金 ,V为C14相稳定元素 ,而Co、Fe、Cu则为C15相稳定元素。取代量较少时 ,Cr为C15相稳定元素 ,取代量增加时 ,C15相稳定作用减弱。Ti元素为C14相稳定元素 ,Ti对Zr的部分取代将导致合金主相结构转变为C14型Laves相。合金化元素对ZrMn2 合金的相组成的影响与元素的电子浓度和原子尺寸不同有关     

电弧熔炼Cr-40Ti-20Nb三元合金的组织与压缩性能

采用真空非自耗电弧熔炼的方法制备了Cr-40Ti-20Nb(原子分数)合金.利用光学显微镜(OM),X射线衍射(XRD),扫描电镜(SEM)分析了合金不同凝固位置处的相组成和组织形态.结果表明,合金的凝固组织主要是由Laves相Cr2(Nb,Ti)枝晶组织及丁i的固溶体组成.同时对合金的显微硬度和压缩性能进行了测试,显微硬度值在6 112～7 350MPa之间,比Laves相Cr2Nb的显微硬度低20％.另外室温压缩屈服强度可达1 334-1 524 MPa,与采用多种合金化元素的Cr-12Nb-4Re-2Al合金相当,这表明Ti元素的添加不仅可以改变Laves相Cr2Nhb合金的凝固组织,而且对其塑性也有很大程度的改善.     

新型钛钒系贮氢电极合金

研究了新型钛钒系贮氢电极合金Ti0.8Zr0.2V2.665Mn0.535Cr0.8Ni的相结构、微观组织及电化学性能。XRD及EDS分析表明：铸态合金主要由C14 Laves相母体和树枝晶的钒基固溶体相组成，同时由于成分偏析的缘故，合金中还存在少量的TiNi基的第三相。热处理使得合金中C14 Laves相及钒基固溶体相的晶胞参数和晶胞体积增大，促进合金成分的均匀化，同时极大地改善了合金电极的综合电化学性能。     

（V30Ti35Cr25Fe10）97．5Si2．5合金的结构与吸放氢性能

采用XRD，SEM和PCT测试研究了（V30Ti35Cr25Fe10）97.5Si2.5（at％）合金的组织结构与吸放氢性能。结果表明：合金由BCC相和C14 Laves相组成，BCC相含量为75％，晶胞参数为α=0．3021nm，Laves相含量为25％，晶胞参数为α=0．4920nm和c=0．7996nm。由于含有大量的Laves相，合金具有良好的活化性能，室温下不需孕育期就可以快速吸氢，5min内达到吸氢饱和状态，饱和吸氢量达到2．98％（质量分数，下同）。在一定氢压下，合金的容量可由合金中BCC相和Laves相的容量按组分的含量进行线性组合而成。     

Pulverization mechanism of the multiphase Ti–V-based hydrogen storage electrode alloy during charge/discharge cycling

Pulverization is an important key factor for the electrochemical cycle stability of many hydrogen storage alloys. In this paper, the pulverization mechanism of the multiphase Ti–V-based hydrogen storage alloy which mainly consists of a V-based solid solution phase with the BCC structure and a C14 Laves phase is studied based on a sample material of the Ti_0.8Zr_0.2V_2.7Mn_0.5Cr_0.6Ni_1.25Fe_0.2 alloy. The microstructure of the alloy and the morphology change of the alloy electrode during the charge/discharge process were observed by transmission electron microscope, scanning electron microscope and atomic force microscope, etc. The effect of mechanical properties of the V-based phase and the C14 Laves phase on the pulverization behavior of the Ti–V-based alloy is discussed. The results show that microcracks initially occur at the phase boundary of the V-based phase and the C14 Laves phase and then extend to the C14 Laves phase in the charge/discharge process. The phase boundary is composed of a Ti segregated amorphous layer with a thickness of about 90 nm, mismatching with the crystallized V-base phase and C14 Laves phase. The toughness of the C14 Laves phase is much lower and the hardness is higher than that of the V-based phase. The weak bonding strength of the phase boundary, the lower toughness of the C14 Laves phase and the large volume expansion/contraction of the C14 Laves phase during charge/discharge cycling are the main factors that cause the pulverization of the Ti–V-based alloy.     

VFe合金取代TiCr1.8合金中部分Cr对其结构和储氢性能的影响

采用XRD、PCT和TG-DSC方法研究了VFe合金取代TiCr1.8合金中部分Cr对其结构与吸放氢性能的影响.结果表明:随VFe取代Cr的量的增加,合金的相组成逐步由Laves相转变为BCC相,而且BCC相的晶胞参数随合金中VFe含量的增加而增大;合金的最大储氢量随VFe含量的增加而升高,合金的最大储氢量可达到5.2/结构单元,质量比约3.4%;但合金的可逆储氢量却随合金中VFe含量的增加先升高后降低;氢在BCC相的TiCr1.2(VFe)0.6合金中有两种具有不同结合能的储存位置.     

Cr含量对CrxMoNbTiZr系高熵合金组织与性能的影响

采用真空电弧熔炼的方法制备了Cr_xMoNbTiZr系高熵合金(x=0, 0.5, 1, 1.5)。利用X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)、显微硬度计以及电化学工作站研究了Cr含量对该高熵合金结构、组织、硬度和耐蚀性能的影响。结果表明,Cr的添加使合金由单相BCC结构转变为富Zr相与富Mo-Nb相的双相BCC结构,随着Cr含量增加,在富Zr相中还有富Cr的Laves相析出;Cr_1.5MoNbTiZr合金具有最高硬度765.53 HV,这是由于第二相析出强化、固溶强化与高熵合金晶格畸变的共同作用;Cr的加入增加了Cr_xMoNbTiZr系高熵合金在质量分数为3.5%NaCl溶液中发生腐蚀倾向,但降低了该系高熵合金的腐蚀速率,同时发现Cr的添加存在一个临界值来保证合金的抗点蚀能力,超过这个临界值合金就会更容易发生点蚀现象。     

Microstructure and properties of novel quinary multi-principal element alloys with refractory elements

Five equiatomic alloys(Ti Zr Hf VNb, Ti Zr Hf VTa, Ti Zr Nb Mo V, Ti Zr Hf Mo V and Zr Nb Mo Hf V) composed of five elements with high melting temperature, respectively were prepared by arc-melting to develop a novel high temperature alloy. The five alloys exhibit different dendritic and interdendritic morphologies. The Ti Zr Hf VNb, Ti Zr Hf VTa and Ti Zr Nb Mo V alloys formed disordered solid solution phases with body-centered cubic structure, and exhibited high compressive strength and good plasticity. The Ti Zr Hf Mo V and Zr Nb Mo Hf V alloys are composed with Laves phase(Hf Mo2) and disordered solid solution phases with body-centered cubic structure. The Ti Zr Hf Mo V and Zr Nb Mo Hf V alloys are harder and more brittle than the other three alloys due to the existence of hard and brittle Laves phases. At high temperatures, the strength decreases to below 300 MPa for the Ti Zr Hf VNb and Ti Zr Hf Mo V alloys. Solution strengthening is the primary strengthening mechanism of the Ti Zr Hf VNb, Ti Zr Hf VTa and Ti Zr Nb Mo V alloys, and brittle Laves phase is the main cause for the low ductility of the Ti Zr Hf Mo V and Zr Nb Mo Hf V alloys.     

Cr部分替代Mn对Ti—Zr—V—Mn—Ni贮氢合金相结构、显微组织及电化学性能的影响

研究了Cr部分替代Mn对Ti-Zr-V-Mn-Ni贮氢合金相结合,显微组织及电化学性能的影响。结果表明,随着Cr的加入,合金电极的循环稳定性得到明显改善,但电极放电容量有所下降,XRD及EDS分析表明,合金主要由六方结构的C14Laves母相和立方结构的TiNi型第二相构成,Cr替代后,合金中出现了立方结构的V-Cr固溶相,金相显微组织显示,铸态和退火态合金均由连续的C14Laves相基体以及TiNi型树枝晶第二相组成。     

Combined ab initio and experimental study of A2 + L21 coherent equilibria in the Fe–Al–X (X = Ti,Nb, V) systems

A combined theoretical and experimental study of ordering and phase separation in α-Fe alloys in the Fe–Al–X (X = Ti, Nb, V) systems is presented. The theoretical part is dedicated to the assessment of the BCC-based phase equilibrium diagram in the iron-rich zone of the ternary systems via a truncated cluster expansion, through the combination of Full-Potential-Linear augmented Plane Wave (FP-LAPW) electronic structure calculations and of Cluster Variation Method (CVM) thermodynamic calculations in the irregular tetrahedron approximation. The stability and the solid solubility of Al in the Fe₂X Laves phases are also included in the discussion of the ternary BCC ground state diagrams. The approach was employed in order to explore particular vertical sections of the ternary systems where a coherent two-phase microstructure can be generated with an optimal combination of volume fraction of Fe₂AlX (L2₁) Heusler type precipitates and Al content in the α-Fe (A2) matrix. The results indicate that in the Fe–Al–Ti and Fe–Al–V systems there are two kinds of phase separations of the BCC phase, (A2+ L2₁) and (B2 (FeAl structure) + L2₁). A tie-line separates both two-phase fields that shrinks and moves toward the Fe-X binary system while its direction remains almost parallel as the temperature increases. Selected experiments were performed on three alloys of the Fe–Al–Ti system belonging to vertical sections that contain this tie-line. The microstructure and composition of the matrix and precipitate phases were characterized by transmission electron microscopy (TEM) and Energy Dispersive Spectroscopy (EDS), the theoretical predictions were borne out.     

Ti_（0.10）Zr_（0.15）V_（0.35）Cr_（0.10）Ni_（0.30）-10% LaNi_3复合物的电化学储氢特性及协同效应

为了改善钛钒基固溶体合金的电催化活性和动力学性能,采用两步电弧熔炼法制备储氢复合合金Ti0.10Zr0.15V0.35Cr0.10Ni0.30–10%LaNi3,利用X-射线衍射、场发射扫描电镜-能谱、电化学阻抗谱和恒流充放电测试技术系统研究该储氢复合合金电极的电化学性能与协同效应。结果表明：该复合合金的主相是BCC结构的钒基固溶体相和六方结构的C14Laves相,在复合过程中生成了第二相;复合合金电极的综合电化学性能较母体合金有显著改善;复合合金电极的活化周期为5周,最大放电容量为362.5mA·h/g,在233K时放电能力为65.84%;在活化、复合、任意循环及高、低温和高倍率放电过程中,该储氢复合合金电极的放电容量均存在协同效应;该复合合金电极的电荷转移电阻和交换电流密度均存在协同效应。     

元素Ti对贮氢合金ZrMn0．7V0．2CO0．1Ni1．2相结构和电化学性能的影响

研究了元素Ti对贮氢电极合金ZrMn0.7V0.2Co0.1Ni1.2的相结构、相组成以及电化学性能的影响。结果表明，对于合金Zr1-xTix(Mn0.7V0.2Co0.1Ni1.2)，其母体合金的主相为C15型Laves相，并含有少量的非Laves相Zr7M10；但随着掺Ti量的增加，合金中出现C14型Laves相，而且其含量逐渐增加；在x=0．1～0．2时，合金中还出现少量的TiNi相，而在x=0．4～0．5时，非Laves相Zr7M10和TiNi相全部消失，说明元素Ti大量的掺杂抑制了第二相的产生：而且随着Ti含量的增加，合金中的C15型和C14型Laves相的晶格常数逐渐减小。电化学测试结果发现，当含Ti量x=0．2时，合金有最大放电容量Cmax为354mAh／g，在放电电流为300mAh／g条件下，高倍率放电性能比母体合金提高了15％。     

Effect of rapid solidification on the structural and electrochemical properties of the Ti–V-based hydrogen storage electrode alloy

The structural and electrochemical properties of the as-cast and rapidly solidified Ti_0.8Zr_0.2V_2.4Mn_0.48Cr_0.72Ni_0.9 alloys were studied. Both the as-cast and the rapidly solidified alloys were mainly composed of a C14 Laves phase matrix with hexagonal structure and a V-based solid solution phase with body centered cubic (BCC) structure. The V-based solid solution phase showed very fine dendrites in the rapidly solidified alloy instead of the large dendrites as observed in the as-cast alloy. In addition, the content of the C14 Laves phase in the alloy decreased greatly after rapid solidification. Electrochemical measurements indicated that the rapidly solidified alloy had a lower discharge capacity, a slower activation rate, a worse high rate dischargeability, a smaller exchange current density and limiting current density, but an improved cycle life compared with that of the as-cast alloy.     

Microstructure of NiCoAlFeCuCr multi-component systems synthesized by mechanical alloying

The present study uses the mechanical alloying method to produce series of binary to senary alloys based on Ni, Co, Al, Fe, Cu, Cr. Milling times are 0, 10, 20 and 30 h and experiments are performed in a high energy ball mill. The results of this investigation show that an FCC solid solution is formed in all the studied systems, but a different phase formation response is presented in each system. A mixture of FCC and BCC solid solutions in quaternary to senary systems, is formed for short milling times. Apparently, the dissolution rate of Fe and Cr into the FCC solid solution, is low. Moreover, it is observed that additions of these elements promote the formation of BCC solid solution, which is stable at temperatures up to ?1273 K. Finally, it is observed that the heat treated products present a mixture of FCC and BCC solid solutions with lattice parameters close to those found in the milled products.     

Hydrogenation properties and crystal structures of Ti−Mn-V BCC solid solution alloys

We have proposed new hydrogen absorbing alloys of the ‘Laves phase related BCC solid solution alloy’, the hydrogen capacity of which reaches almost double that of conventional rare-earth based AB₅ alloys. We have reported the hydrogen absorbing properties of Ti−V−Mn, Ti−V−Cr and T−V−Mn−Cr alloys. It has been accepted that the crystal structural change of BCC hydrogen absorbing alloys is the same as that of V metal. The mono-hydride (H/M=1) of V metal has a BCT structure and the di-hydride (H/M=2) has an FCC structure. However, we recently found that the Ti−V−Mn alloy shows different behaviors in phase transformation with hydrogenation to V metal. We found three hydride phases with a BCC, a deformed FCC and an FCC structure in the Ti−V−Mn solid solution alloy-H₂ system. The deformed FCC hydride phase has not yet to our knowledge been reported. The lattice constant of the deformed FCC was 0.407 nm, one axis of which is reduced by about 4%. Its single-phase region appeared at a hydrogen content between 0.8 H/M and 1.0 H/M in absorption at 298 K. The lower plateau observed due to formation of the deformed FCC hydride phase gives an increase of effective hydrogen capacity by decreasing hydrogen remaining in the alloy in the desorption process. This article based on a presentation made in the symposium “The 2nd KIM-JIM Joint Symposium: Hydrogen Absorbing Materials”, held at Hanyang University, Seoul, Korea, October 27–28, 2000 under the auspices of The Korean Institute of Metals and Materials and The Japan Institute of Metals.