急冷对Ti_(0.32)Cr_(0.345)V_(0.25)Fe_(0.03)Mn_(0.055)合金储氢性能的影响

为了研究急冷对储氢合金残余氢量的影响,利用真空电弧熔炼炉和铜模喷铸制备了Ti_(0.32)Cr_(0.345)V_(0.25)Fe_(0.03)Mn_(0.055)合金,采用XRD、PCT(压力-容量-温度)、TG/DTA等手段分析了急冷对储氢合金吸放氢性能的影响。结果表明,铸态合金和急冷合金均由BCC固溶体主相和Laves第二相组成;急冷对首次吸氢动力学行为影响较大,由铸态时的化学反应控制变为急冷时的新相晶核形成长大控制;急冷后,合金吸放氢平台压得到提高,且吸氢起始点左移,但吸放氢滞后性增大。TG/DTA曲线表明,急冷并没有改变合金的残余氢量,但氢化物放氢温度升高。     

铁取代部分铬对TiVCrMn合金储氢性能的影响

38Ti-30V-18Mn-14Cr合金具有比较大的吸氧量,但是其放氢平台太低,尤其是有效放氢量太少.Fe有利于合金放氢平台提高,所以本文研究了Fe取代部分Cr对该合金的吸/放氢性能的影响.X射线衍射(XRD)分析表明,随Fe取代Cr的量的增加,合金的相组成经由单一的体心立方(bcc)相逐渐转变为bcc与Laves两相共存,合金bcc相的晶格常数和晶胞体积减小.吸放氢性能曲线表明,Fe取代Cr后合金的最大吸氢量降低,但是合金的放氢平台显著升高,合金的有效放氢量增大.对于38Ti-30V-18Mn-10cr4Fe合金,在298 K吸氢、353 K放氢的条件下,有效放氢量达到最大为1.51%.     

还原氧化石墨烯负载次氯酸镧纳米复合物催化增强Mg-Al合金储氢性能

在氩气保护下采用热处理并结合机械合金化制备Mg-Al合金,同时以氧化石墨烯(GO)、LaCl_3以及NaOH作为原材料,通过化学还原法制备还原氧化石墨烯负载次氯酸镧(LaClO@rGO)纳米复合物,并通过扫描电镜(SEM)、压力-成分-温度(PCT)、差示扫描量热仪(DSC)等手段表征LaClO@rGO纳米复合物的添加对Mg-Al合金储氢性能的影响。研究表明Mg-Al合金主要由Mg_(17)Al_(12)和Mg组成,Mg-Al合金的初始吸/放氢温度分别为150. 3和277. 4℃,添加LaClO@rGO复合材料后,合金的初始吸/放氢温度下降到97. 0和206. 8℃,比纯Mg-Al合金初始吸放氢温度分别下降了53. 3和70. 6℃,且Mg-Al-LaClO@rGO复合材料在250℃即可实现可逆吸放氢。此外,在LaClO@rGO纳米材料的催化作用下,在温度为150℃时,Mg-Al-LaClO@rGO吸氢速率相当于Mg-Al合金吸氢速率的6. 37倍;在温度为275℃时,Mg-Al-LaClO@rGO复合材料的脱氢速率相当于Mg-Al合金脱氢速率的3. 0倍。显然,LaClO@rGO纳米复合材料的添加,不仅能提高Mg-Al合金的可逆储氢性能,还能提高Mg-Al合金的吸放氢动力学性能。     

Ti/Cr比对(VFe)50Ti26-xCr24+x(0≤x≤2.0)储氢合金吸放氢性能的影响

为研究不同Ti/Cr比对(VFe)50Ti26-xCr24+x(0≤x≤2.0)储氢合金吸放氢性能的影响规律,采用FeV80中间合金制备了低成本储氢合金并系统研究了储氢合金的吸放氢性能及组织结构.PCT及XRD实验结果表明:随着Ti/r比的降低(x的增加),合金的吸放氢量均呈现减小的趋势,放氢平台压则不断增大,所有的合金均由主相BCC及稀土氧化物CeO2相组成,主相BCC的晶格常数随着Ti/Cr比的降低而减小.     

成型压力对Mg-Ni-La/Ce合金吸放氢动力学的影响

为提高镁基储氢合金的体积储氢密度和增加材料导热性能，需要对合金粉末进行压片处理。制备了不同成型压力下直径为10 mm的片状Mg₈₇Ni₁₀La₃和Mg₈₇Ni₁₀Ce₃合金，研究成型压力对合金体积储氢密度、膨胀特性和吸放氢反应动力学性能的影响。结果表明，在760～1900 MPa下，合金片的表观密度达到粉末的两倍左右；考虑吸放氢循环过程中的体积膨胀，第4次吸氢过程中两种合金的储氢体积密度仍然高于70 g·L^-1,1520 MPa的成型压力下Mg₈₇Ni₁₀Ce₃合金片具有最大体积储氢密度为86.3 g·L^-1。两种合金在4次循环吸放氢后的轴向和径向膨胀为10%左右，体积膨胀约为35%，合金颗粒的粉化是造成膨胀的主要原因。与粉末状材料相比，合金片的首次活化比较困难，吸放氢动力学性能有部分下降；随着吸放氢循环次数的增加，压片成型对合金吸放氢动力学的影响...     

锆钒铁合金的吸放氢性能及相结构研究

研究了活化温度和活化保温时间对ZrVFe合金吸放氢性能的影响,并采用XRD分析ZrVFe合金吸放氢反应前后的相结构变化。测定了ZrVFe合金吸放氢过程的P-C-T曲线,采用范德霍夫方程计算出合金吸、放氢的标准焓ΔH~Θ和标准熵ΔS~Θ,并由此外推出该合金在室温下的吸氢平衡压在10~(-8)Pa左右,放氢平衡压在10~(-10)Pa左右。此外,ZrVFe合金还有良好的抗粉化性能和抗空气毒化性能。     

Ce替代Y对Y_(1-x)Ce_xFe_2(x=0,0.15,0.25和0.50)合金吸氢性能的影响

利用磁悬浮感应熔炼法制备了Y_(1-x)Ce_xFe_2(x=0,0.15,0.25,和0.50)合金,通过X射线衍射分析(XRD)、扫描电镜(SEM)、电子探针(EPMA)和定容法等测试方法,研究了Ce替代Y对Y_(1-x)Ce_xFe_2合金吸氢性能的影响。研究表明,Y_(1-x)Ce_xFe_2合金为多相结构,主相为MgCu_2型结构的YFe_2相,同时还含有Pu Ni3型结构的YFe_3第二相,且Ce元素有效替代了合金中的Y元素;当x≦0.25时,随着Ce替代量的增加,合金中YFe_3相增多,且合金的吸氢动力学性能和吸放氢循环稳定性得以改善,初始吸氢平衡时间t0.9由48 s降低至12 s,经7次吸放氢循环后,稳定吸氢容量由0.409%升高至0.598%(质量分数),吸氢容量衰减率由79%降低至55%,但合金初始吸氢容量有所下降;这主要归因于YFe_3相较之于YFe_2相结构更加稳定,但其吸氢容量更低;当x=0.50时,合金的吸氢容量及吸放氢循环稳定性均同步下降,此时合金中的YFe2相增多,合金吸氢后歧化反应加剧。因此,在Y_(1-x)Ce_xFe_2中,Ce对Y的替代量以小于0.50为宜。     

Ce替代La对合金LaNi4.5Al0.5储氢性能及热力学的影响

金属Ce替代LaNi_4.5Al_0.5合金中的La用以提高金属吸/放氢热力学性能。通过研究合金La_1-xCe_xNi_4.5Al_0.5(x=0～0.4)的相结构、储氢热力学以及吸/放氢动力学发现,所制备的合金主相为六方晶系LaNi₅相;随着Ce替代量的增加(x=0～0.4),合金晶体结构中a轴呈现减小的趋势、c轴及各向异性(c/a)呈现出先增大后减小再增大的趋势;储氢性能测试表明,随着Ce替代量的增加,合金的吸/放氢平台压升高,最大储氢量减小;合金吸/放氢反应热优化程度与各向异性(c/a)呈现出相同趋势,当x=0.2时,合金吸放氢反应焓变分别降低至26.33 kJ/mol和24.30 kJ/mol。     

La_(0.88)Mg_(0.12)Ni_(3.45)与商用AB_5型储氢合金失效行为的对比研究

以实验室熔炼制备的La_(0.88)Mg_(0.12)Ni_(3.45)合金和商用AB5型合金为研究对象,利用形貌、物相、粒度和腐蚀电化学分析手段对比研究了两种合金在气固相和电化学吸放氢循环过程中的结构稳定性、粉化和腐蚀行为特征。结果表明,经过100次的气固相吸放氢试验,La_(0.88)Mg_(0.12)Ni_(3.45)合金中除LaNi_5相以外,其他相均发生了吸氢非晶化。氢致非晶化导致合金可逆吸放氢容量显著降低,并使合金吸氢初段的平台严重倾斜。La_(0.88)Mg_(0.12)Ni_(3.45)合金循环后的粉化较轻,但合金中细小的(LaMg)Ni_2相吸氢后较易剥落,导致部分小颗粒粒度频率的增加。商用AB_5型合金循环后粒度降低更明显,但其粉化过程更为均匀。La_(0.88)Mg_(0.12)Ni_(3.45)合金有更大的腐蚀热力学和动力学倾向,因此电化学循环后腐蚀更加严重。氢致非晶化和腐蚀是La_(0.88)Mg_(0.12)Ni_(3.45)合金失效的主要原因。     

钛对镁基电子电气贮氢材料性能的影响

为了研究钛对Mg_2Ni贮氢材料性能的影响,在Mg_2Ni合金中添加不同含量的合金元素钛,并进行了显微组织、吸放氢性能和循环稳定性的测试与分析。结果表明:钛的添加有利于细化晶粒,提高材料的吸放氢性能和循环稳定性。与不添加钛(Mg_2Ni)相比,添加8.233%钛时(Mg_2NiTi_(0.2))的平均晶粒尺寸减小55.63%、最大吸氢量增大47.37%、充放电循环20次后放电容量衰减率减小48.80%、吸氢饱和时间和放氢平台压力基本不变。Mg_2Ni贮氢材料中钛的含量优选为8.233%。     

储氢合金电极失效的机理分析及研究进展

分析了储氢合金电极失效的四种基本理论,即合金颗粒粉化、元素氧化、吸氢非晶化与释氢晶化、电化学腐蚀机制,并综述其研究进展,提出延缓合金电极容量衰减,改善其循环性能的有效控制途径.     

A comparison study of hydrogen storage performances of SmMg11Ni alloys prepared by melt spinning and ball milling

The melt spinning(MS) and ball milling(BM) technologies are thought to be efficient to prepare nanostructured Mg and Mg-based alloys for improving their hydrogen storage performances. In this paper, two technologies, viz. melt spinning and ball milling, were employed to fabricate the SmMg_(11)Ni alloy. The structure and hydrogen storage performance of these two kinds of alloys were researched in detail. The results reveal that the as-spun and milled alloys both contain nanocrystalline and amorphous structures. By means of the measurement of PCT curves, the thermodynamic parameters of the alloys prepared by MS and BM are ΔN_(Ms)(des) = 82.51 kJ/mol and ΔH_(BM)(des) = 81.68 kJ/mol, respectively, viz.ΔH_(MS)(des) ΔH_(BM)(des). The as-milled alloy shows a larger hydrogen absorption capacity as compared with the as-spun one. The as-milled alloy exhibits lower onset hydrogen desorption temperature than the as-spun one. As to the as-milled and spun alloys, the onset hydrogen desorption temperatures are557.6 and 565.3 K, respectively. Additionally, the as-milled alloy shows a superior hydrogen desorption property than the as-spun one. On the basis of time that required by desorbing hydrogen of 3 wt% H_2, the as-milled alloy needs 1488.574,390 and 192 s corresponding to hydrogen desorption temperatures 593,613,633 and 653 K, while the as-spun alloy needs 3600,1020,778 and 306 s corresponding to the same temperatures. The dehydrogenation activation energies of the as-milled and spun alloys are 100.31 and105.56 kJ/mol, respectively, the difference of which is responsible for the much faster dehydriding rate of the as-milled alloy.     

MmNi5-x(CoAlMn)x/Mg纳米晶复合储氢合金的吸氢性能

研究了机械合金化制备的ＭｍＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ／Ｍｇ纳米晶复合储氢合金的吸氢特性。通过测定不同镁含量的ＭｍＮｉ５－ｘ（ＣｏＡｌＭｎ）ｘ／Ｍｇ纳米晶复合储氢合金的吸氢ＰＣＴ曲线,考察了镁含量对其吸氢特性的影响。根据对吸氢速度的测定研究了机械合金化对储氢合金的吸氢动力学特性的影响。机械合金化制备的纳米晶复合储氢合金的活化性能与ＭｍＮｉＭ５－ｘ（ＣｏＡｌＭｎ）ｘ铸态合金相比有较大的提高,不需活化或只需一次活化即可吸氢,吸氢量及吸氢的动力学性能与铸态合金相比也有很大的提高。最后对机械合金化形成的纳米晶吸氢特性进行了分析。     

Phase evolution,hydrogen storage thermodynamics and kinetics of ternary Mg_(90)Ce_5Sm_5 alloy

Greatly stable thermodynamics and sluggish kinetics impede the practical application of Mg-based hydrogen storage alloys.The modifications of composition and structure are important strategies in turning these hydrogen storage properties.In this study,Mg-based Mg_(90)Ce_5 Sm_5 ternary alloy fabricated by vacuum induction melting was investigated to explore the performance and the reaction mechanism as hydrogen storage material by X-ray diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM) and pressure-composition isotherms(PCI) measurements.The results indicate that the Mg-based Mg_(90)Ce_5 Sm_5 ternary alloy consists of two solid solution phases,including the major phases(Ce,Sm)5 Mg_(41) and the minor phases(Ce,Sm)Mg_(12).After hydrogen absorption,these phases transform into the MgH2 and(Ce,Sm)H_(2.73) phase,while after hydrogen desorption,the MgH2 transforms into the Mg phase,but the(Ce,Sm)H2.73 phases are not changed.The alloy has a reversible hydrogen capacity of about 5.5 wt% H_2 and exhibits well isothermal hydrogen absorption kinetics.Activation energy of 106 kJ/mol was obtained from the hydrogen desorption data between 573 and 633 K,which also exhibits the enhanced kinetics compared with the pure MgH2 sample,as a result of bimetallic synergy catalysis function of(Ce,Sm)H_(2.73) phases.The rate of hydrogen desorption is controlled by the release and recombination of H_2 from the Mg surface.Furthermore,the changes of enthalpy and entropy of hydrogen absorption/desorption were calculated to be-80.0 kJ/mol H_2,-137.5 J/K/mol H_2 and 81.2 kJ/mol H_2,139.2 J/K/mol H_2,respectively.     

Hydrogen Storage Performances of REMg11Ni (RE = Sm,Y) Alloys Prepared by Mechanical Milling

This study adopted mechanical milling to prepare Mg-based REMg₁₁Ni (RE = Sm, Y) hydrogen storage alloys. The alloy structures were examined by X-ray diffraction and transmission electron microscopy. The isothermal hydrogenation thermodynamics and kinetics were determined by an automatic Sievert apparatus. The non-isothermal dehydrogenation performance of the alloys was tested by differential scanning calorimetry and thermogravimetry at different heating rates. The results showed a nanocrystalline and amorphous tendency for the alloys. The YMg₁₁Ni alloy exhibited a larger hydrogen absorption capacity, faster hydriding rate, and lower temperature of onset hydrogen desorption than the SmMg₁₁Ni alloy. The hydrogen desorption temperatures of the REMg₁₁Ni (RE = Sm, Y) alloys were 557.6 K and 549.8 K (284.6 °C and 276.8 °C), respectively. The hydrogen desorption property of the RE = Y alloy was found superior to the RE = Sm alloy based on the time required to absorb 3 wt pct H₂, i.e., the time needed by the RE = Y alloy was reduced to 1106, 456, 363, and 180 s, respectively, corresponding to the hydrogen desorption temperatures of 593 K, 613 K, 633 K, and 653 K (320 °C, 340 °C, 360 °C, and 380 °C), compared to 1488, 574, 390, and 192 s for the RE = Sm alloy under identical conditions. The dehydrogenation activation energies were 100.31 and 98.01 kJ/mol for the REMg₁₁Ni (RE = Sm, Y) alloys, respectively, which agreed with those of the RE = Y alloy showing a superior hydrogen desorption property.

     

AB5型含Mn储氢合金的研究综述

文章评述了近年来人们对提高AB5型含Mn储氢合金综合性能所进行的研究。通过综述AB5型含Mn稀土系储氢合金Mn在合金中的作用及Mn含量变化、显微结构等对储氢合金的影响,得出储氢合金中Mn对吸氢平台压力、储氢容量、吸放氢速率、循环寿命的影响。通过利用Mn元素对B侧元素的部分或全部替代或Mn被其它元素替代,可以对AB5型储氢合金进行更深入研究,从而进一步提高其综合性能。     

循环伏安法测定纳米晶贮氢合金中氢扩散系数

用双辊快淬法制备了纳米晶稀土贮氢合金,XRD图谱表征为结晶较好的CaCu5六方结构,Scherrer公式计算晶粒大小约为40nm。利用循环伏安法测定了纳米晶稀土贮氢合金电极中的氢扩散系数(DH=1.67×10-7cm2/s),由于纳米晶粒具有较高的结晶度和细小的晶粒尺寸,高密度晶界为氢在合金内部的扩散提供快速通道,提高了贮氢合金的吸放氢效率,从而提高了氢的扩散性能,使电极中氢的扩散系数增大。     

V-Ti-Fe储氢合金的真空精炼

采用真空感应炉对金属热还原法制备的V-Ti-Fe合金进行精炼,考察金属铈对精炼效果的影响。结果表明,铈可有效脱除合金中的氧杂质,减少合金内的富钛相和硅偏聚相,降低合金的成分偏析,促进合金的吸氢活化。随铈用量的增加,脱氧效果也逐渐增强,储氢容量得到提升,当铈添加量达到合金用量的5%时,氧含量降到了0.05%,最大吸氢量和有效放氢量分别达到3.36%和1.85%。     

MmNi5-x(CoAlMn)x/Mg纳米晶复合储氢合金 的吸氢性能

研究了机械合金化制备的MmNi