Mn含量对(V60Ti22.4Cr5.6Fe12)100-xMnx(0≤x≤3)合金吸放氢性能的影响

系统研究了采用FeV80中间合金制备的低成本(V60Ti22.4Cr5.6Fe12)100-x Mnx(0≤x≤3)合金的吸放氢性能及微观组织结构。XRD及PCT测试结果表明,随着Mn含量的增加,合金的晶格常数减小,放氢平台压先升高后降低;吸氢量随Mn含量的增加不断降低,而Mn含量的增加对放氢量没有显著影响。当Mn含量为2.5 at%时,合金室温下的放氢平台压达到最大值0.14 MPa,吸氢量为3.64%(质量分数,下同),放氢量为2.00%。SEM及EDS分析表明,不同Mn含量的合金均由bcc主相、富钛二相及稀土氧化物相组成,且Mn主要存在于合金的bcc主相中,而在富钛二相中分布相对较少。     

TiV1．35Cr1．35-x．Mnx（x=0～0．45）合金的相结构及储氢特性

系统研究了TiV1．35Cr1．35-x．Mnx（x=0,0．15,0．25,0.35,0．45)合金的相结构及储氢性能。XRD分析表明,所有合金均为体心立方(b.c.c．)结构的单一固溶体相,其晶胞常数随Mn含量的增加而逐渐减小。储氢性能测试表明,用Mn部分取代Cr后,合金的活化性能变差,25℃最大吸氢量有所下降,但合金的吸放氢压力滞后减小,放氢压力平台变得平坦,100℃有效放氢量和放氢率也随着Mn含量的增加先升后降,并在x=0.35时达到最大值。     

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。     

V-Ti-Cr-Fe合金的储氢性能研究

研究了V（30％）-Ti（15％～55％）-Cr（7％～43％）-Fe（2％～18％）（原子分数，下同）四元合金的储氢性能。结果表明：V-Ti-Cr-Fe四元合金的吸氢量与有效吸氢量主要由Ti／（Cr＋Fe）比决定，当Ti／（Cr＋Fe）=1时，合金具有最好的吸放氢性能。随着Ti／（Cr＋Fe）比升高，合金的晶格常数增大，氢化物的生成焓增大，放氢平台压力降低。在298K时，V30Ti35Cr25Fe10合金的吸氢量达到3．6％（质量分数，下同），有效吸氢量达到2．0％。     

Zr替代Ti对Ti19.5V40Mn16.2Cr9.8Ni14.5合金的影响Ⅰ:结构及储氢性能

为改善Ti-V基固溶体型储氢合金的电化学性能,使用少量的Zr部分取代Ti19.5V40Mn16.2Cr9.8Ni14.5合金中的Ti,并采用XRD,SEM以及PCT等测试手段研究替代前后合金微观结构和储氢性能的变化情况.通过XRD和SEM分析表明,(Ti1-xZrx)19.5V40Mn16.2Cr9.8Ni14.5(x=0,0.1,0.15,0.2,0.25,0.3)合金均是由Ti-V基BCC相和C14 Laves相组成.但Zr的部分替代明显增加了C14Laves相的含量,并使Ti-V基BCC相在减少的同时由树枝状变成了被C14Laves相包围的岛状.PCT曲线显示:随着Zr替代量的增加.合金的吸放氢平台不断下降,而合金的吸放氢量先有所增加后又逐渐减小.这说明适量提高C14 Laves相的含量对增加Ti-V基固溶体型储氢合金的吸放氢能力有一定的促进作用.     

硼添加对(Ti0.65Zr0.35)1.10(V0.5Mn0.3Cr0.4Ni0.8)Bx合金结构和电化学性能的影响

采用X射线衍射仪、扫描电镜和电化学测试设备,研究添加不同含量硼对(Ti0.65Zr0.35)1.10(V0.5Mn0.3Cr0.4Ni0.8)Bx (x=0,0.01,0.05,0.1,0.2)储氢合金组织结构和电化学性能的影响。结果表明,由于硼的添加,合金中出现了不易形成氢化物的棒状VB相,降低了合金的可逆放电容量,提高了合金的活化性能、循环稳定性和合金的倍率性能。分析表明,主要是由于棒状VB相增加了氢在合金中的扩散通道,增加了相界面,减小了合金在充放电过程中的晶格应力。合金电极的反应阻抗随着硼含量的增加而减小,合金的倍率性能和循环性能明显优化。     

球磨改性处理对Ti0．9Zr0．1Mn1．5合金相结构及储氢性能的影响

系统研究了Ti0．9Zr0．1Mn1．5储氢合金经不同时间（t=0min，10min，30min，60min）球磨改性处理后对其相结构及储氢性能的影响。结构分析表明，Ti0．9Zr0．1Mn1．5合金在球磨改性处理前后均由单一的六方结构的C14型Laves相组成；随着球磨时间的延长，合金粉的平均粒度减小，并出现了部分团聚现象。储氢性能测试表明，铸态合金经4次吸放氢循环后活化，室温最大吸氢量和有效放氢量分别为209．3ml／g和157．6ml／g，放氢率为75．3％；随着球磨时间的延长，合金的活化性能得到改善，室温最大吸氢量和有效放氢量均先升后降，且都在球磨30min时达到相应最高值231．4ml／g和203．8ml／g，放氢率达到88．1％。由此可见，适当的球磨改性处理能有效地改善Ti0．9Zr0．1Mn1．5合金的综合储氢性能。     

Ti／Cr比对xTi-18Mn-（50-x）Cr-32V合金吸／放氢性能的影响

研究了xTi-18Mn-（50-x）Cr-32V（z=36，34，32，30，28）合金的吸／放氢性能。结果表明：随Ti／Cr比值的减小，合金的晶格常数和晶胞体积减小，这虽然导致合金的最大吸氢量降低，但是合金的有效放氢量增大，且合金PCT曲线的滞后系数降低。合金（110）面法线方向上晶粒尺度的大小是影响合金放氢平台斜率系数的因素之一。对于32Ti．18Mn．18Cr．32V合金，在273K吸氢、353K放氢的条件下，有效放氢量达到1．72％（质量分数），具有实用价值。     

Zr替代Ti对Ti19．5V40Mn16．2Cr9．8Ni14．5合金的影响结构及储氢性能

为改善Ti—V基固溶体型储氢合金的电化学性能，使用少量的Zr部分取代Ti19.5V40Mn16.2Cr9.8Ni14.5合金中的Ti，并采用XRD，SEM以及PCT等测试手段研究替代前后合金微观结构和储氢性能的变化情况。通过XRD和SEM分析表明，（Ti1-xZrx）19.5V40Mn16.2Cr9.8Ni14.5（x=0，0．1，0．15，0．2，0．25，0．3）合金均是由Ti-V基BCC相和C14 Laves相组成。但Zr的部分替代明显增加了C14 Laves相的含量，并使Ti-V基BCC相在减少的同时由树枝状变成了被C14 Laves相包围的岛状。PCT曲线显示：随着Zr替代量的增加。合金的吸放氢平台不断下降，而合金的吸放氢量先有所增加后又逐渐减小。这说明适量提高C14 Laves相的含量对增加Ti—V基固溶体型储氢合金的吸放氢能力有一定的促进作用。     

Ti1.2Fe＋x%Mg（x=1,3,5）合金的贮氢特性

在TiFe合金中添加少量的IIA族轻金属元素Mg，并且使Ti侧过化学计量，组织Ti1.2F3 x%（质量分数，下同）Mg（x=1,3,5)试验合金，研究了该系列合金的储氢特性。结果表明，Ti1.2F3 3%Mg和Ti1.2F3 5%Mg合金在室温下，经2次吸放氢操作即能完全活化，前者的储氢量为213ml/g，且具有较小的压力滞后和平台斜率，适合作为内氢燃料电池氢源储氢材料。X射线分析发现，所有试验合金的主相均为TiFe相，而合金显微组织显示，Mg以弥散颗粒分布于合金基体，并讨论了Mg的添加和Ti过量对合金活化性能和储氢容量的影响机制。     

Effect of Ti content on the hydrogen storage properties of Zr_（1-x）Ti_xMn_2Ce_（0.015） alloys

The effect of Ti content on the hydrogen storage properties of Zr1-xTixMn2 Ce0.015(x = 0,0.2,0.3,0.5) alloys was studied by X-ray diffraction,scanning electron microscopy and pressure-composition(p-c) isotherm measurement.All of the alloys mainly consist of C14-type Laves and CeO2 phases.As the Ti content increases,the lattice parameters of the Laves phase decrease and the unit cell shrinks anisotropically,the total hydrogen absorption capacity decreases but the reversible hydrogen desorption capacity of the alloys increases,and the equilibrium pressure of the alloys increases but the plateau becomes sloping.The changes of hydrogen storage properties of Zr1-xTixMn2 Ce0.015 alloys are related to the differences in both atomic radius and hydrogen affinity between Ti and Zr elements.     

Effect of Ti content on the hydrogen storage properties of Zr1-xTixMn2Ce0.015 alloys

The effect of Ti content on the hydrogen storage properties of Zr1-xTixMn2 Ce0.015 (x = 0,0.2,0.3,0.5) alloys was studied by X-ray diffraction, scanning electron microscopy and pressure-composition (p-c) isotherm measurement. All of the alloys mainly consist of C14-type Laves and CeO2 phases. As the Ti content increases, the lattice parameters of the Laves phase decrease and the unit cell shrinks anisotropically, the total hydrogen absorption capacity decreases but the reversible hydrogen desorption capacity of the alloys increases, and the equilibrium pressure of the alloys increases but the plateau becomes sloping. The changes of hydrogen storage properties of Zr1-xTixMn2 Ce0.015 alloys are related to the differences in both atomic radius and hydrogen affinity between Ti and Zr elements.     

稀土组成对贮氢合金La0．8（1-x）Ce0．8x（PrNd）0．2B5性能的影响

系统研究了A侧稀土元素中Ce含量对AB5犁贮氢合金La0．8（1-x)Ce0．8x(PrNd)0．2B5的结构、热力学性能、电化学性能和动力学性能的影响。结果表明：Ce含量对合金的结构基本上没有明显的影响，合金的晶胞参数a、c及晶胞体积与Ce的含量的变化呈线性关系；随着Ce含量增加，合金的吸放氢平台压力升高，滞后效应减小，吸氢量减小，合金氢化物的热力学稳定性变差：Ce含量的变化对合金的电化学活化速度影响很小，但Ce含量的增加可以明显提高合金的放电中值电位，改善合金的高倍率、高功率放电性能和动力学性能。     

Effect of manganese addition on hydrogen storage performance of vanadium-based BCC hydrogen storage alloys

The effect of manganese addition on hydrogen storage performance of vanadium-based BCC alloys was investigated by measuring mainly pressure-composition (P−C) isotherms at 303K. Annealing heat-treatment was also considered in selected cases. The XRD patterns showed BCC single phase in all the alloys. With increasing Mn content, the lattice parameters decreased linearly, thus resulting in an increase in plateau pressure and a reverse effect on maximum hydrogen storage capacity. However, an effective hydrogen storage capacity as high as 1.92 wt.% was achieved at x=0.075. V−Ti−Mn alloys showed a surprisingly flat desorption plateau, but lots of absorbed hydrogen cannot desorb at ambient temperature. Although V_0.44Ti_0.20Cr_0.12Mn_0.12Fe_0.12 alloy did not show the first plateau, both the maximum and effective hydrogen storage capacities were very low.     

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%.     

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 …     

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.     

La0.7Y0.3Ni3.4-xMnxAl0.1(Х=0~0.5)储氢合金微观结构和电化学性能

采用真空电弧熔炼及热处理的方法制备La0.7Y0.3Ni3.4-ХMnХAl0.1(Х=0~0.5)合金,通过XRD、SEM、EDS和电化学测试等方法,系统地研究了Mn替代Ni对合金微观组织、储氢和电化学性能的影响规律。结果表明,退火合金微观组织由主相Ce2Ni7型相和杂相PuNi3型、CeNi3型及Ce5Co19型相组成,Ce2Ni7型主相的丰度随Mn含量增加呈先增大后减小变化规律。当Х=0.2时,主相的丰度达到最大值89.03%。增加Mn的含量有助于缓解合金的氢致非晶化倾向。随着Mn含量的增加,合金电极的放电容量逐渐升高,而充放电循环稳定性却逐渐降低,合金电极的最大放电容量和最佳循环稳定性分别为308.6mAh/g与95.09%。合金电极的反应动力学分析结果表明,氢原子在合金体相中的扩散为合金电极高倍率放电性能的动力学控制步骤。     

Effect of Manganese substitution on hydrogen storage properties of LaNi4.25-xAl0.75Mnx alloy

The effect of Mn substitution on phase structure, hydrogen hydriding/dehydriding properties (plateau pressure and slope) and reaction heat enthalpy of LaNi4.25-xAl0.75Mnx alloys (x=0, 0.25, 0.35, 0.45, 0.55 and 0.65) were studied.The experimental results show that all LaNi4.25-xAl0.75Mnx alloys have single phase and have the same hexagonal structure as that of LaNi5 alloy (CaCu5 type, P6/mmm).With increasing Mn substitution content, the cell parameters of LaNi4.25-xAl0.75Mnx alloy greatly increase, but the maximum hydrogen storage capacity and the equilibrium absorption pressure of LaNi4.25-xAl0.75Mnx alloy decrease from 1.38 wt.% to 1.18 wt.% and from 1.61 to 0.0712 MPa, respectively.Moreover, the hydrogen pressure plateau slope factor σ increases from 0.014 to 0.18, but the hysteresis factor is nearly constant.The heat enthalpy absolute value |ΔHplat| increases from 46.7 kJ·mol-1 H2 to 56.1 kJ·mol-1 H2 as the Mn content x increases from 0 to 0.65.