Design of Zr-based AB_2 type hydrogen storage alloys

1　INTRODUCTIONPresently ,therearetwokindsofhydrogenstor agealloys (AB5andAB2 )usedinnickel metalhy dride (Ni/MH)battery .AB2 typehydrogenstoragealloyhasworseactivationperformanceandlowerini tialcapacitythoughitscapacityishigherandlifeislongerthanAB5alloy .Atthesametime ,AB2 typehydrogenstoragealloyismoreexpensivethanAB5typehydrogenstoragealloy .AlltheaboveaspectsembarrasstheactualapplicationofAB2 typehydrogenstoragealloy .PropertiesofAB2 typehydrogenstor agealloy ,suchascapacity ,…     

Hydrogen solubility and diffusion studies of Zr-based AB2 alloys and sol–gel encapsulated AB2 alloy particles

Hydrogen solubility and hydrogen diffusion coefficients have been studied in Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5, Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55 and (Ti_0.1Zr_0.9)_1.1Mn_0.9V_0.1Fe_0.5Co_0.5 in the temperature range 450–650 °C with hydrogen gas pressure up to 100 mbar and hydrogen concentration up to 0.03 hydrogen atoms per formula unit. H₂ absorption is exothermic, and the values of partial enthalpy of solution per H atom are in the range from −370 ± 10 meV to −466 ± 50 meV. The silica embedded AB₂ alloy particles have been prepared by sol–gel technique. P–C isotherms of encapsulated AB₂ alloy particles have been obtained in the pressure and temperature ranges 0–30 bar and 30–100 °C, respectively. Diffusion of H interstitials in sol–gel encapsulated Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Ni_0.5, (Ti_0.1Zr_0.9)_1.1Mn_0.9V_0.1Fe_0.5Ni_0.5 and (Ti_0.1Zr_0.9)_1.1Mn_0.9V_0.1Fe_0.5Co_0.5 alloy particles have been studied between 500 and 650 °C with H₂ gas pressure up to 100 mbar and H concentration up to 0.014 H atoms per formula unit. Diffusion coefficient (D) of H interstitials has been determined for all these samples from the kinetics of hydrogen absorption. The activation energies have been calculated from temperature dependence of diffusion coefficient and the values are in the range 416 ± 15–897 ± 50 meV.     

Rare earth-Mg-Ni-based hydrogen storage alloys as negative electrode materials for Ni/MH batteries

This review is devoted to new rare earth-Mg-Ni-based (R-Mg-Ni-based) hydrogen storage alloys that have been developed over the last decade as the most promising next generation negative electrode materials for high energy and high power Ni/MH batteries. Preparation techniques, structural characteristics, gas-solid reactions and electrochemical performances of this system alloy are systematically summarized and discussed. The improvement in electrochemical properties and their degradation mechanisms are covered in detail. Optimized alloy compositions with high discharge capacities, good electrochemical kinetics and reasonable cycle lives are described as well. For their practical applications in Ni/MH batteries, however, it is essential to develop an industrial-scale homogeneous preparation technique, and a low-cost R-Mg-Ni-based electrode alloy (low-Co or Co-free) with high discharge capacity, long cycle life and good kinetics.     

First-principles calculations and experimental studies of Sn-Zn alloys as negative electrode materials for lithium-ion batteries

The physical characters and electrochemical properties of various phases in a Sn-Zn electrode,such as formation energy,plateau potential,specific capacity,as well as volume expansion,were calculated by the first-principles plane-wave pseudo-potential method based on the density functional theory.Sn-Zn films were also deposited on copper foils by an electroless plating technique.The actual composition and chemical characters were explored by scanning electron microscopy (SEM),X-ray diffraction (XRD),plasma atomic emission spectrometry (ICP),and constant current charge/discharge measurements (CC).The results show that separation phases with tin and zinc including a small quantity of Cu6Sn5 phase were obtained,the initial lithium insertion capacity of the Sn-Zn film was 661 mAh/g,and obvious potential plateaus of about 0.4 V and 0.7 V were displayed,which is in accordance with the results of theoretical calculations.The capacity of the Sn-Zn film decreased seriously with the increase of cycle number.     

球磨时间和转速对球磨法制备纳米锑粉的影响

以250 μm大小的锑粉为原料,在添加相同含量蒸馏水和烷基酚聚氧乙烯醚的条件下,采用湿法机械球磨的方式制备出不同类型的锑基粉末.采用XRD、TEM及FT-IR对制备的锑基粉末的结构、形貌及粒径大小进行了表征分析,研究了球磨时间和球磨转速对锑粉制备的影响.结果表明:当锑粉原料中加入1 ml/g蒸馏水和0.2 ml/g OP-1O湿磨时,球磨转速为150r/min、球磨时间为18 h可制备出分散良好、粒径分布均匀、平均粒径约为10 nm的锑粉.     

湿法球磨工艺对CeO2粒度分布及抛光性能的影响

抛光粉粒度与其抛光性能有密切关系,然而粒度相同的抛光粉,粒度分布的不同对其抛光性能也具有重要影响.为了探究粒度分布对抛光性能的影响,以粒径较大的CeO2粉为原料,使用不同球磨设备对CeO2粉进行细化,设置不同的球磨工艺参数并添加不同的助剂,获得中位粒径D50=1 μm,具有不同粒度分布的CeO2料液,添加一定量分散剂调配成固含量10％(质量分数)的抛光液.用9B双面抛光机对K9玻璃进行抛光,记录玻璃单位时间质量减少量,并利用原子力显微镜测量抛光表面粗糙度.结果 表明,设置不同的球磨工艺可以对CeO2粒径分布进行调控,CeO2粒度分布较窄时,具有较高的抛光去除率MRR,粒度分布适中时,兼具抛光效率与表面质量.使用行星式搅拌球磨机,选用直径为3mm的磨珠、球料比为5∶1,抛光机转速为30 rpm,浆液流速为30 rpm、并在球磨介质中添加质量比为0.1％的聚丙烯酸钠作为助剂时,可获得最低的表面粗糙度Ra=0.849nm.     

Changes in the microstructure and hydrogen storage properties of Ti-Cr-V alloys by ball milling and heat treatment

Changes in the microstructure and hydrogen storage properties of Ti-Cr-V alloys were investigated after a combination of ball milling and heat treatment. Two different sets of balls and vials made of tungsten carbide (WC) and stainless steel (STS) were used for milling the samples. Ball milling using WC balls and vials induced WC contamination, and it caused compositional changes in the matrix during heat treatment. When STS balls and vials were used, meanwhile, no peak of the second phase caused by contamination was found in the X-ray diffraction (XRD) data. In the case of the sample that completed only the milling process, the crystallite size calculated from the XRD data, 20-30 nm, agreed well with the grain size obtained from transmission electron microscopy (TEM). On the other hand, for the sample that was heat treated after milling, the strain decreased from 0.74% to 0.18%, the crystallite size increased to 70-80 nm, and the grain size grew up to the level of hundreds of nanometers. The changes in microstructure induced by the ball milling and heat treatment influenced the hydrogen storage properties, such as plateau pressure, hysteresis, and phase transformation with hydrogen absorption. Thus, the relationship between the microstructure and hydrogen storage properties can be explained.     

Effect of electroless plating nickel treatment on electrode properties of Zr-based AB_2 type alloy

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Corrosion and degradation behavior of Zr-based AB2 alloy electrodes during electrochemical cycling

Zr-based AB₂ Laves phase alloys are promising materials for the negative electrodes in Ni–MH batteries. In this work, their cyclic durability and corrosion behavior in the electrolyte were systematically investigated using instrumental analyses such as ICPS, XRD, SEM, EPMA, XPS as well as PCT and specific surface area measurement.     

Synthesis process of Mg–Ti BCC alloys by means of ball milling

The synthesis process of Mg–Ti alloys with a BCC (body centered cubic) structure by means of ball milling was studied by X-ray diffraction and various microscopic techniques. The morphology and crystal structure of Mg–Ti alloys changed with increase of milling time. During ball milling of Mg and Ti powders in molar ratio of 1:1, firstly, plate-like particles stuck on the surface of the milling pot and balls. After these plate-like particles fell off from the surface of the milling pot and balls, spherical particles with the mean diameter of 1 mm, in which concentric layers of Mg and Ti were disposed, were formed. These spherical particles were crushed into spherical particles with the diameter of around 10 μm by introduction of cracks along the boundaries between Mg and Ti layers. Finally, the Mg₅₀Ti₅₀ BCC phase with the lattice parameter of a = 0.342(1) nm and the grain size of 3 nm was formed. During milling of Mg and Ti to synthesize the BCC alloy, Mg and Ti were deformed mainly by the basal plane slip and the twinning deformation, respectively. Ti acted as abrasives for Mg which had stuck on the surface of the milling pot and balls. The BCC phase was found after Mg dissolved in Ti.     

Effect of ball milling time on microstructure and properties of Laves phase NbCr2 alloys synthesized by hot pressing

Laves phase NbCr2 alloys with a composition of Nb-66.7Cr (molar fraction, %) were prepared by mechanical alloying and hot pressing. The microstructures and properties of the Laves phase NbCr2 alloys, prepared from elemental niobium and chromium powders under various ball milling time by hot pressing at 1 250 ℃ for 0.5 h, were investigated. The results indicate that if the ball milling time is longer than 40 h, the synthesizing reaction of Laves phase NbCr2 can be accomplished much sufficiently. Then the nearly full-dense Laves phase NbCr2 alloys can be prepared by hot pressing from ball milled powders with more than 40 h. The hot pressing sample with homogeneous and fine microstructure made from 40 h ball milled powders has the optimum microstructure and properties. It has a relative density of 98.1%, Vickers hardness of 11.4 GPa, compress strength of 1 981 MPa and fracture toughness of 4.82 MPa·m1/2. The effect of fine grain toughening is fully realized.     

固化球磨纳米晶粉末制备块体超细晶Mg-3Al-Zn合金(英文)

采用粉末冶金技术制备块体超细晶Mg-3Al-Zn合金。首先采用球磨Mg、Al、Zn混合粉末来制备纳米晶粉末,所得的粉末的平均晶粒尺寸为45nm。随后将球磨好的粉末封入铝包套内,分别在室温和633K温度下,在真空烧结炉内进行真空热压。然后将烧结后的样品在423K下挤压以进行进一步的致密化处理。结果表明:致密后的冷压样品的晶粒尺寸为180nm,而热压坯的晶粒尺寸为600nm,冷压样品的屈服强度达464MPa;超细晶镁合金的强化机制主要是细晶强化,这主要是由于HCP结构的材料晶粒尺寸对材料的影响更为明显。固化后冷压样品的最终密度为(1.777±0.006)g/cm3,而热压样品的最终密度为(1.800±0.006)g/cm3。     

Effect of ball milling time on microstructures and mechanical properties of mechanically-alloyed iron-based materials

The microstructures and mechanical properties of an iron-based alloy (Fe-13Cr-3W-0.4Ti-0.25Y-0.30O) prepared by mechanical alloying were investigated with scanning electron microscope, optical microscope, X-ray diffractometer and hardness tester. The results show that the particle size does not decrease with milling time because serious welding occurs at 144 h. The density of the alloy sintered at 1 523 K is affected by the particle size of the powder. Finer particles lead to a high sintered density, while the bulk density by using particles milled for 144 h is as low as 70%. In the microstructures of the annealed alloy, large elongated particles and fine equiaxed grains can be detected. The elongated particle zone has a higher microhardness than the equiaxed grain area in the annealed alloys due to the larger residual strain and higher density of the precipitated phase.     

Ni-MH电池负极材料贮氢合金的表面处理

综述了Ｎｉ－ＭＨ电池负极材料贮氢合金的表面处理方法,包括它们对合金电极（或Ｎｉ－ＭＨ电池）性能的影响、作用机理及其操作工艺。     

Preparation of pure Higher Manganese Silicides through wet ball milling and reactive sintering with enhanced thermoelectric properties

A simple and effective process is used to synthesize undoped Higher Manganese Silicides (HMS), involving ball milling under soft conditions to obtain homogeneous mixtures of constituting elements, and subsequent spark plasma sintering for a direct solid state reaction. For comparison purpose, the ball milling step is carried out under both dry and wet conditions using n-hexane as the liquid medium, Analysis of the granulometry demonstrates that the wet milling process in n-hexane results in finer particles, thus improving the reaction rate later on. According to X-ray diffraction and scanning microscopy, materials produced via wet milling and spark plasma sintering contain only HMS while dry milled samples contain MnSi impuritties. The Seebeck coefficient of the wet milling sample is 20% higher, while its electrical resistivity is 23% lower than those of the dry milling one over the whole temperature range. Moreover, the thermal conductivity was reduced up to 30% when using n-hexane as milling media. The maximum thermoelectric figure of merit obtained is 0.55 at 850 K, a high value for undoped HMS.     

Structure and high-temperature oxidation behaviour of Cu-Ni-Fe alloys prepared by high-energy ball milling for application as inert anodes in aluminium electrolysis

Cu_xNi_85−xFe₁₅ (0 ? x ? 85 wt.%) compounds were prepared by mechanical alloying. Monophased face centered cubic (fcc) Cu-Ni-Fe alloys were obtained after 10 h of milling for x varying from 0 to 50, whereas bi-phased compounds fcc Cu-Ni-Fe + body centered cubic (bcc) Fe were formed with richer-Cu compounds. Their oxidation kinetics in air at 750 °C is parabolic for all compositions and increases drastically for x > ∼30. A stable anode for aluminium electrolysis in low-temperature (700 °C) KF-AlF₃ electrolyte was obtained for 65 ? x ? 85. However, a substantial increase of the Cu contamination in produced aluminium was observed for x > 70.     

球磨方式对纳米晶Mg2FeH6储氢材料合成与放氢性能的影响

分别应用Uni-Ball-Mill 5和XQM-4变频行星式球磨机将Mg粉和Fe粉在氢气中直接球磨合成三元储氢相Mg2FeH6。采用球磨罐中的氢压降、X射线衍射谱、扫描电镜、热分析、吸放氢测试等测试手段研究了不同球磨方式对纳米晶Mg2FeH6储氢材料的合成结果。结果表明,XQM-4变频行星式球磨机球磨150 h,Mg2FeH6相的产率（质量分数）接近70%;在100 kPa氢压下,380℃放氢量为2.66%,粉末呈片状,晶粒在7 nm以下。而采用Uni-Ball-Mill 5球磨机P2方式球磨270h,Mg2FeH6相的产率仅为39.1%,100 kPa氧压下,350℃放氢量为1.15%,粉末呈球状。两者的差别可能源于前一种球磨方式具有更高的球磨合金化效率。     

冷-热处理对Zr基块体非晶合金结构和性能的影响

传统晶态材料构件或装备在低温环境中会出现可动部分卡死、龟裂、特性改变甚至脆性断裂等现象。低温极端条件如温度突变、高应变速率冲击等对材料性能带来的不利影响严重制约了其在低温极端环境领域的应用。块体非晶合金在低温条件下具有强度更高塑性更好的特殊性能,在极地科考以及航空航天等极端条件下具有极大的应用优势。本文以(Zr_0.6336Cu_0.1452Ni_0.1012Al_0.12)₉₇Tm₃块体非晶合金为研究对象,研究冷-热处理时间对块体非晶合金的结构、力学性能和腐蚀性能的影响。结果表明,当处理时间由30 min延长到90 min时,试样的晶化体积分数从2.3%增加到4.0%,屈服强度由1701 MPa增加到1810 MPa。在3.5 wt.% NaCl溶液中,合金具有较小的自腐蚀电流密度与较大的电化学阻抗,这意味着经冷-热处理后的块体非晶合金具有优异的耐腐蚀性能。本研究为块体非晶合金在低温极端环境领域的应用提供了强有力的理论支撑。     

Hydrogen sorption properties of Ti–Cr alloys synthesized by ball milling and cold rolling

Three Ti–Cr alloys with nominal compositions of TiCr_x (x = 2, 1.8 and 1.5) were synthesized by cold rolling and ball milling of as-cast ingots, and their microstructures and hydrogenation properties were studied. X-ray diffraction showed that TiCr_x transformed from a mixture of C14 and C15 Laves phases to a metastable BCC phase after 5 h of ball milling under argon. Cold rolling did not lead to the formation of a metastable BCC phase but only to the reduction of TiCr_x size particles under 20 nm. Surprisingly, the hydrogen absorption/desorption curves of cold rolled and ball milled samples at 323 K were quite similar. This result proves that hydrogen storage properties do not depend only on microstructure and that cold rolling could be an interesting method to synthesize hydrogen storage materials.     

A comparative study on the hydriding kinetics of Zr-based AB2 hydrogen storage alloys

Two kinetic models (Jander model and Chou model) are used to investigate the hydrogen absorption kinetic mechanism of Zr-based AB₂ type Laves phase alloys (Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5, Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55). The analysis shows that the rate-controlling step is the diffusion process at high temperatures in the range from 673 K to 923 K with a low hydrogen concentration (solid solution phase). Both models can well describe the experimental data but Chou model is preferred. Chou model is simpler and easier to use for analyzing the experimental results. The activation energies calculated using Chou model with the least square method are 29.3 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5, 43.8 kJ/mol H₂ for Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and 48.5 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55, which are close to the values reported in the literature (28.3 kJ/mol H₂ for Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.5Co_0.5 and 40.3 ± 1.5 kJ/mol H₂ for both Ti_0.1Zr_0.9(Mn_0.9V_0.1)_1.1Fe_0.5Ni_0.5 and Ti_0.1Zr_0.9Mn_0.9V_0.1Fe_0.55Ni_0.55).