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Electrochemical hydrogen storage characteristics of La_(0.75-x) M_xMg_(0.25)Ni_(3.2)Co_(0.2)Al_(0.1)(M=Zr,Pr;x=0,0.1) alloys prepared by melt spinning

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Rare Metals 2012年第5期31卷 -页

作者： ZHANG Yanghuan YANG Tai CAI Ying hou zhonghui REN Huiping ZHAO Dongliang Key Laboratory of Integrated Exploitation of Baiyun Obo Mutti-Metal Resources Inner Mongolia University of Science and Technology Baotou 014010 China Department of Functional Material Research Central Iron and Steel Research Institute Beijing 100081 China

In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology was used to fabricate the La_(0.75-x)M_xMg_0.25Ni_3.2Co_0.2Al_0.1 (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)_2Ni_7 and LaNi_5 as well as a residual phase LaNi_2 . 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.

关键词： A_2B_7-type electrode alloy element substitution melt spinning electrochemical performance

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Structure and hydrogen storage characteristics of as-spun Mg-Y-Ni-Cu alloys

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Journal of Materials Science & Technology 2019年第8期35卷 1727-1734页

作者： Yanghuan Zhang Pengpeng Wang zhonghui hou Zeming Yuan Yan Qi Shihai Guo Key Laboratory of Integrated Exploitation of Baiyun Obo Multi-Metal Resources Inner Mongolia University of Science and Technology Baotou 014010 China Department of Functional Material Research Central Iron and Steel Research Institute Beijing 100081 China

Experimental alloys with compositions of Mg(25-x)YxNi9Cu(x=0,1,3,5,7)have been successfully prepared through melt spinning *** phase compositions and microstructures were measured by X-Ray diffraction(XRD)and high-resolution transmission electron microscopy(HRTEM).The de-/hydrogenation properties were measured by utilizing Sievert apparatus,differential scanning calorimetry(DSC)and thermal gravimetric analyzer(TGA)connected with a H2 *** Arrhenius and Kissinger methods were adopted to calculate their dehydrogenation activation *** results show that hydrogen absorption kinetics of the alloys notably decline while their hydrogen desorption kinetics conspicuously improve with spinning rate *** dehydrogenation activation energy markedly decreases with spinning rate increasing,which makes the hydrogen desorption kinetics *** thermodynamic parameters(H and S absolute values)clearly decrease with spinning rate *** hydrogen absorption capacity exhibits different trends with spinning rate ***,hydrogen absorption capacity increases at the beginning and declines later for Y1 alloy,but that of Y7 alloy always decreases with spinning rate growing.

关键词： Mg-Ni-based alloy Thermodynamics Activation energy Melt spinning Hydrogen storage kinetics

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An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg12-type Alloys Synthesized by Mechanical Milling

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Journal of Wuhan University of Technology(Materials Science) 2018年第2期33卷 278-287页

作者：张羊换 WANG Jinglong ZHANG Peilong ZHU Yongguo hou zhonghui SHANG Hongwei Key Laboratory of Integrated Exploitation of Baiyun Obo Multi-Metal Resources Inner Mongolia University of Science and Technology Baotou 014010 China Department of Functional Material Research Central Iron and Steel Research Institute Beijing 100081 China Beijing Whole Win Materials Sci. & Tech. Co. Ltd. Beijing 100083 China

Nanocrystalline and amorphous LaMg_（12）-type LaMg_（11）Ni ＋ x wt% Ni（x = 100, 200） alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter（DSC） connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability（HRD） and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.

关键词： LaMg12 alloy mechanical milling activation energy hydrogen storage kinetics

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Research on micro-structure and catalysis properties of nanosized Ce_(1–x)(Fe_(0.5)Eu_(0.5))_xO_(2–δ) solid solutions

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Journal of Rare Earths 2017年第1期35卷 63-70页

作者： ZHANG Guofang XU Jianyi hou zhonghui WANG Qingchun School of Material and Metallurgy Inner Mongolia University of Science and Technology Baotou 014010 China Key Laboratory of lntergrate Exploration of Baiyun Obo Multi-metal Resources Inner Mongolia University of Science and Technology Baotou 014010 China

Nanosized Fe^3＋ and Eu^3＋ codoped CeO2 solid solutions were synthesized via hydrothermal method. The crystalline structure of Ce1-x（Fe0.5Eu0.5）xO2-δx=0.00–0.30） solid solutions was carried out by the X-ray diffraction technique, and the spectrum features were identified by UV-Vis and Raman spectroscopy, respectively. It was observed that the cell parameters were first increased then decreased by increasing the doped ions content. The phase separation was detected when the dopant concentration reached to x=0.30. UV-Vis spectrum showed that the width of the band gap gradually reduced by increasing the doped content, and the solid solubility was determined to be x=0.20. The Raman technique displayed that the peak position of F2g mode gradually shifted to lower frequencies from 465 cm^–1 for x=0.00 to 440 cm^–1 for x=0.20. The catalytic effects of Ce1-x（Fe0.5Eu0.5）xO2-δsolid solutions on the electrochemistry properties of Mg2Ni/Ni were measured by mixing them together via ball milling technique. The electrochemical properties of the Mg_2Ni/Ni-Ce1-x（Fe0.5Eu0.5）xO2-δcomposites showed that the maximum discharge capability Cmax and the cycle stability were improved obviously. Meanwhile, the EIS characteristic also indicated that the doped solid solutions could enhance the rate of charge transfer on the surface of alloy. The catalytic effect of the solid solutions was speculated to rely on both the concentration of oxygen vacancies and the cell volumes of the solid solutions.

关键词： solid solution hydrothermal Mg2Ni catalysis effect electrochemistry property rare earths

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Gaseous hydrogen storage properties of Mg-Y-Ni-Cu alloys prepared by melt spinning

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Journal of Rare Earths 2019年第7期37卷 750-759页

作者： Yanghuan Zhang Yaqin Li Wei Zhang Zeming Yuan zhonghui hou Yan Qi Shihai Guo Key Laboratory of Integrated Exploitation of Baiyun Obo Multi-Metal Resources Inner Mongolia University of Science and TechnologyBaotou 014010China Institute for Advanced Materials and Technology University of Science and Technology BeijingBeijing 100083China Department of Functional Material Research Central Iron and Steel Research InstituteBeijing 100081China

For purpose of promoting the hydrogen absorption and desorption thermodynamics and kinetics properties of Mg-Ni-based alloys, partially substituting Y and Cu for Mg and Ni respectively and melt spinning technique were applied for getting Mg25-xYxNi9 Cu(χ = 0-7) alloys. Their microstructures and phases were characterized with the help of X-ray diffraction and transmission electron microscopy. Their hydrogen absorbing and desorbing properties were tested by a Sievert apparatus, DSC, and TGA, which were connected with a H2 detector. In order to estimate the dehydrogenation activation energy of alloy hydride, both Arrhenius and Kissinger methods were applied for calculation. It is found that their hydriding kinetics notably declines, however, their hydrogen desorption kinetics conspicuously improves, with spinning rate and Y content increasing. Their hydrogen desorption activation energy markedly decreases under the same constraint, and it is found that melt spinning and Y substituting Mg improve the real driving force for dehydrogenation. As for the tendency of hydrogen absorption capacity,it presents an elevation firstly and soon after a decline with the rising of spinning rate, however, it always lowers with Y content growing. With Y content and spinning rate increasing, their thermodynamic parameters(△H and △S absolute values) visibly decrease, and the starting hydrogen desorption temperatures of alloy hydrides obviously lower.

关键词： Mg-Ni-based alloy Melt spinning Activation energy Hydrogen storage kinetics Thermodynamics Rare earths

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Electrochemical Hydrogen Storage Performance of the Nanocrystalline and Amorphous Pr-Mg-Ni-based Alloys Synthesized by Mechanical Milling

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Journal of Wuhan University of Technology(Materials Science) 2021年第1期36卷 116-126页

作者： hou zhonghui YUAN Zeming FENG Dianchen SUN Hao ZHANG Yanghuan Department of Functional Material Research Central Iron and Steel Research InstituteBeijing 100081China College of Material and Metallurgy Inner Mongolia University of Science and TechnologyBaotou 014010China

The PrMg12-type composite alloy of PrMg_(11)Ni + x wt% Ni (x=100,200) with an amorphous and nanocrystalline microstructure were synthesized through the mechanical *** of milling duration and Ni content on the microstructures and electrochemical hydrogen storage performances of the ball-milled alloys were methodically *** ball-milled alloys obtain the optimum discharge capacities at the first *** Ni content dramatically enhances the electrochemical property of *** time varying may obviously impact the electrochemical performance of these *** discharge capacities show a significant upward trend with milling duration prolonging,but milling for a longer time more than 40 h induces a slight decrease in the discharge capacity of the x=200 *** milling duration increases,the cycle stability clearly lowers,while it first declines and then augments under the same condition for the x=200 *** high-rate discharge abilities of the ball-milled alloys show the optimum values with milling time varying.

关键词： PrMg_(12)-type alloy mechanical milling nanocrystalline and amorphous electrochemical performance electrochemical kinetics

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Gaseous and Electrochemical Hydrogen Storage Properties of Nanocrystalline Mg<sub>2</sub>Ni-Type Alloys Prepared by Melt Spinning

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Materials Sciences and Applications 2011年第3期2卷 141-150页

作者： Zhihong Ma Bo Li Huiping Ren zhonghui hou Guofang Zhang Yanghuan Zhang 不详

A partial substitution of Ni by Cu has been carried out in order to improve the hydrogen storage characteristics of the Mg2Ni-type alloys. The nanocrystalline Mg20Ni10-xCux (x = 0, 1, 2, 3, 4) alloys are synthesized by the melt-spinning technique. The structures of the as-cast and spun alloys have been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM). The electrochemical performances were evaluated by an automatic galvanostatic system. The hydrogen absorption and desorption kinetics of the alloys were determined by using an automatically controlled Sieverts apparatus. The results indicate that the substitution of Cu for Ni does not alter the major phase Mg2Ni. The Cu substitution significantly ameliorates the electrochemical hydrogen storage performances of alloys, involving both the discharge capacity and the cycle stability. The hydrogen absorption capacity of alloys has been observed to be first increase and then decrease with an increase in the Cu contents. However, the hydrogen desorption capacity of the alloys exhibit a monotonous growth with an increase in the Cu contents.

关键词： Mg2Ni-Type Alloy Cu Substitution Melt Spinning Hydrogen Storage Property

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Hydrogen Absorption and Electrochemical Properties of As-Quenched Nanocrystalline Mg20Ni10 – xCux (x = 0 – 4) Alloys

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Materials Sciences and Applications 2010年第3期1卷 168-176页

作者： Jinliang Gao zhonghui hou Qilu Ge Dongliang Zhao Shihai Guo Yanghuan Zhang 不详

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

关键词： Mg2Ni-type Alloy Rapid Quenching Nanocrystalline Hydrogen Absorption Electrochemical Properties

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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)

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稀有金属材料与工程 2013年第11期42卷 2201-2206页

作者：张羊换蔡颖杨泰侯忠辉张国芳赵栋梁内蒙古自治区白云鄂博矿多金属资源综合利用重点实验室内蒙古包头014010 钢铁研究总院北京100081

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... 详细信息

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。

关键词： A2B7型合金元素替代金属快淬电化学动力学

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快淬工艺对Mg_2Ni型合金气态及电化学贮氢动力学的影响

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稀有金属材料与工程 2012年第12期41卷 2199-2204页

作者：张羊换王煜张国芳李霞侯忠辉赵栋梁内蒙古科技大学内蒙古自治区白云鄂博矿多金属资源综合利用重点实验室内蒙古包头014010 钢铁研究总院北京100081

用铸造及快淬工艺制备Mg2Ni型Mg2-xLaxNi(x=0,0.2,0.4,0.6)贮氢合金。用XRD、SEM、HRTEM分析铸态及快淬态合金的微观结构,合金的气态贮氢动力学性能用自动控制的Sieverts设备测试,并用程控电池测试仪测试合金的电化学贮氢动力学。结果发... 详细信息

用铸造及快淬工艺制备Mg2Ni型Mg2-xLaxNi(x=0,0.2,0.4,0.6)贮氢合金。用XRD、SEM、HRTEM分析铸态及快淬态合金的微观结构,合金的气态贮氢动力学性能用自动控制的Sieverts设备测试,并用程控电池测试仪测试合金的电化学贮氢动力学。结果发现,La替代Mg明显地改变Mg2Ni型合金的相组成。当x≤0.2时,La替代Mg不改变合金的主相Mg2Ni,但出现少量的LaMg3及La2Mg17相。当La替代量x≥0.4时,合金的主相改变为(La,Mg)Ni3+LaMg3。快淬含La合金显示了以非晶相为主的结构,表明La替代Mg提高了Mg2Ni型合金的非晶形成能力。合金的气态及电化学吸放氢动力学对La含量及快淬工艺敏感,适当的快淬处理可以提高合金的气态及电化学贮氢动力学,但获得最佳贮氢动力学的快淬工艺与合金的成分密切相关。

关键词： Mg2Ni型合金快淬 La替代Mg 贮氢动力学

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