(LaCa3)0.5-xMg1+4xNi9(x=0,0.02,0.04,0.06,0.08,0.1)合金微观结构及储氢性能研究

AB₃型La-Mg-Ni系列储氢合金由于储氢容量优异、放电容量高、活化快等优势受到储能领域的关注.采用真空感应熔炼法制备了(LaCa₃)_0.5-xMg_1+4xNi₉(x=0,0.02,0.04,0.06,0.08,0.1)合金,表征合金的微观结构并测试储氢合金性能差异,研究合金A侧元素比例对合金性能影响的内在机理.合金活化性能受Mg元素取代量的影响明显,活化吸放氢速率随着Mg质量分数的增加先增加后减小.随着Mg替代量的增加,合金的最大吸放氢容量分别由1.866%和1.311%提高到1.972%和1.732%,吸放氢焓变绝对值分别由15.71 kJ/mol和17.88 kJ/mol降低到8.88 kJ/mol和9.28 kJ/mol,其热稳定性降低,这对改善热力学性能有积极作用.     

新型储氢材料Li-Mg-N-H体系的储放氢性能研究

采用机械球磨LiNH2/MgH2混合物(摩尔比2/1.1)制备一种新型储氢材料Li-Mg-N-H.在氩气保护下,将样品分别球磨2 h(1 #)、5 h(2#)和10 h(3#).DSC测试结果表明,3种样品均可在170℃左右开始快速放氢,且随着球磨时间增加,放氢温度呈下降趋势.吸放氢测试结果显示200℃时,样品在6 MPa最大吸放氢量为4.4%,0.1 MPa放氢压力条件下最大放氢容量为3.39%,上述反应在1 h内可完成总量的80%以上;随着球磨时间增加,样品活性增大,首次吸放氢循环即可达到最大容量,但球磨时间过长导致样品吸放氢容量的下降.运用XRD考察了样品吸放氢循环前后的物相变化.     

新法回收废储氢合金性能的研究

针对废储氢合金粉回收提出一种全新的方法,即提炼和冶炼相结合的方法,并研究提炼后的中间合金及再生新合金的性能.经测试,回收后储氢合金的电化学容量达到282 mAh/g,PCT测试固气吸氢量为1.032%(质量分数),X射线测得主体相为CaCu5型六方结构,但其中含有微量杂质相,这有待于对中间合金的提炼工艺做进一步的研究.总之,利用此种方法得到回收后储氢合金的性能与原合金相近,是一种具有广阔发展前景的回收方法.     

氢化燃烧合成制备镁基储氢材料研究进展

氢化燃烧合成(Hydriding Combustion Synthesis,HCS)针对镁基储氢合金的制备而提出,具有设备简单,省能以及产物活性高等特点.将主要介绍本研究小组近期关于HCS产物TEM、SEM、XPS和AES的研究结果,系统阐明其高活性机理.还将介绍HCS镁基储氢合金经过机械球磨改性后吸放氢动力学性能得到大幅改善,373 K,100 s内达到饱和吸氢量物质的量为4.6%的近期研究结果.     

Mg3La化合物储氢性能及Ni的加入对其性能的影响

用X-ray衍射方法(XRD)研究了Mg3La合金和Mg3LaNi0.1合金吸放氢前后的结构变化.Mg3La合金和Mg3LaNi0.1合金在吸/放氢过程中的压力-组成-等温曲线(PCI)和吸氢动力学曲线表明合金能在室温下吸氢,并且具有良好的吸氢动力学特性,能在4 min之内达到饱和吸氢量的90%;其最大吸氢量分别为质量分数2.89%和2.73%.Mg3La金和Mg3LaNi0.1合金的室温吸氢动力学曲线可用Avrami-Erofeev方程拟合,说明吸氢过程符合形核长大机制.同时也计算了Mg3La-H氢化反应的熵和焓.     

Mg-CU合金的储氢特性研究

采用扩散烧结的工艺制备出Mg-Cu多相储氢材料;XRD分析表明烧结产物为Mg2Cu、MgCu2和Cu三相,经20次的吸放氢循环后,该多相材料的储氢量质量分数为2.55%;根据PCT测试结果,得到放氢平衡压和温度的关系式为InP(atm)=-9 006.8/T+17.817,从而得到1.0 atm下的放氢温度为233℃.     

Cr替代量对TiFe合金活化性能与储氢性能的影响

TiFe基储氢合金因其储氢性能良好,原材料价格低廉而广受人们的关注,但活化困难这个问题阻碍了其在工业领域方面的应用.为了研究Cr替代量对于TiFe合金活化过程的影响,使用真空高频电磁感应熔炼炉制备了Ti_1.08Y_0.02Fe_0.8Mn_0.2-xCr_x(x=0,0.02,0.04)合金,测试合金的储氢性能并表征其微观结构.X射线衍射与透射电子显微镜的分析结果表明,试验后的合金中出现的新吸氢相CrH₂可以在试验条件下分解,增加了试验合金的可逆吸氢量.同时,Cr替代Mn显著缩短了合金的活化时间,降低了平台压.且随着Cr替代量的增加,合金的吸氢速率也随之增加.     

LiBH4改善镁吸氢性能的研究

研究了LiBH4对镁吸氢性能的影响,探索出一条不需要活化就能改善镁的储氢性能的途径.实验结果显示,在氩气气氛下球磨质量比为14的LiBH4-Mg混合物1 h后,产物表现出很好的吸氢活性,在300℃下20 min内的吸氢量可达到6.5%,在1 h内可达到7.1%;在250℃和200℃下,1 h内的吸氢量分别可达到6.7%和2.6%.而镁在300℃以下几乎不吸氢.     

La_(1.8)Ca_(0.2)Mg_(14)Ni_3合金在甲苯溶液中球磨改性后的储氢性能

采用在甲苯介质中球磨以改善La1.8Ca0.2Mg14Ni3的储氢性能。随着球磨时间的增加,合金的吸放氢性能得到显著地提高,在20 h达到最高。其在513 K,4.0 MPa氢压下初次活化时,吸氢质量分数达到了3.95%,在3次活化后,300 K时的吸氢质量分数达到3.85%,在613 K,一个大气压的放氢质量分数在900 s内达到了4.92%。通过XRD和SEM分析,球磨后合金颗粒粒径明显减小且有非晶化趋势。在球磨过程中形成了电子络合体(electrondonor-acceptor,EDA)体系。合金颗粒粒径、非晶化程度和EDA共同作用使球磨20 h的合金表现出最优异的吸放氢性能。     

可用于PEMFC燃料电池的钒基固体贮氢材料

介绍了V-Ti-Cr-Fe系列贮氢合金,该系列合金常温无需活化即可快速吸氢,放氢平台压可调,其1 atm以上的可逆吸放氢量超过质量分数2.0%,吸放氢循环500次的容量衰减小于30%.此外,由于利用了廉价的FeV80中间合金,解决了钒基贮氢合金价格昂贵的问题,是目前少有的综合性能优良的贮氢合金,可用于PEMFC燃料电池的高纯氢燃料的贮存载体.     

硼对稀土系AB5型贮氢合金电化学容量及循环寿命的影响

为了提高低钴AB5型贮氢合金的电化学循环稳定性，在MmNi3．8Co0.4Mn0.6Al0．2贮氢合金中加微量的硼．用真空快淬工艺制备了稀土系低钴AB5型MmNi3．8Co0．4Mn0．6Al0．2Bx(x=0，0．1，0．2，0．3，0．4)贮氢合金，分析测试了铸态及快淬态合金的电化学性能及微观结构，研究了硼对铸态及快淬态合金电化学容量及循环寿命的影响．结果表明，硼使铸态及快淬态MmNi3.8Co0.4Mn0．6Al0．2贮氢合金的电化学容量不同程度地降低，但使电化学循环稳定性大幅度提高．硼对电化学性能的影响主要是促进非晶相的形成．     

Influence of Temperature on Electrochemical Performances of Rare Earth Based Hydrogen Storage Material

1 IntroductionRare earth-based hydrogenstorage alloys ofAB5typehave beenthe most major electrode material for small-sizeNi/MHbatteries because of their high discharge capacity,superior highrate capability andfavorable ratio of pricetoperformance. But their electrochemical performances be-come worse when the alloys are applied to large-size Ni/MHbatteries of electric vehicles .Thisfact may be due tothe rising of temperature inside the large batteries causedbythe high electric current of char…     

LaNi_（3.8）Co_（1.1）Mn_（0.1）/TiMn_（1.5）贮氢合金的结构和性能

为了探索一种新的掺杂方式对AB5型贮氢合金贮氢性能的影响,采用熔炼掺杂方法制备La-Ni3.8Co1.1Mn0.1/TiMn1.5（TiMn1.5质量分数为4%、8%）贮氢合金,利用PCTPro-2000气体吸附测量仪研究了合金的气态储氢性能。XRD和SEM分析显示,熔炼掺杂后合金主相为LaNi5相,出现少量（NiCo）3Ti相。P-C-T测试结果表明,（NiCo）3Ti相的出现对合金气态贮氢性能有较大影响,熔炼掺杂后合金吸放氢平台压和滞后效应降低,贮氢容量减少。掺杂TiMn1.5使得合金的氢化物的生成焓由原始合金的-27.35kJ/mol降至-29.14kJ/mol（掺杂质量分数8%的TiMn1.5）,较高温度有利于合金中氢的释放,同时掺杂形成的（NiCo）3Ti相改善了合金吸/放氢动力学性能。     

Effect of VFe addition on hydrogen storage behavior of TiMn1.5-based alloys

The hydrogen absorption and desorption behavior of TiMn1.25Cr0.25 alloys with VFe substitution for partial Mn was investigated at 273, 293 and 313 K. It is found that VFe substitution increases their hydrogen storage capacity, decreases the plateau pressure and the hysteresis factor of their pressure-composition-temperature (PCT) curves. After annealing treatment at 1223 K for 6 h, TiMn0.95Cr0.25(VFe)0.3 alloy exhibits a lower hydrogen desorption plateau pressure (0.27 MPa at 313 K) and a smaller hysteresis factor (0.13 at 313 K); the maximum and effective hydrogen storage capacities (mass fraction) are 2.03% and 1.12% respectively, which can satisfy the demand of hydrogen storage tanks for proton exchange membrane fuel cells (PEMFC).     

AB5型储氢合金电极材料的研究

采用熔体旋转(melt-spinning)技术制备的AB5型储氢合金，用扫描电镜观察合金的显微组织并对合金成分进行了EDX分析，用XRD研究合金结构和晶胞参数及吸氢体胀率，对比快淬态与铸态合金的使用性能．结果表明．快淬态合金性能优于铸态合金．     

Influences of melt spinning on electrochemical hydrogen storage performance of nanocrystalline and amorphous Mg2Ni-type alloys

In order to improve the electrochemical hydrogen storage performance of the Mg₂Ni-type electrode alloys, Mg in the alloy was partially substituted by La, and the nanocrystalline and amorphous Mg₂Ni-type Mg_20−x La _x Ni₁₀ (x=0, 2) alloys were synthesized by melt-spinning technique. The microstructures of the as-spun alloys were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical hydrogen storage properties of the experimental alloys were tested. The results show that no amorphous phase is detected in the as-spun Mg₂₀Ni₁₀ alloy, but the as-spun Mg₁₈La₂Ni₁₀ alloy holds a major amorphous phase. As La content increases from 0 to 2, the maximum discharge capacity of the as-spun (20 m/s) alloys rises from 96.5 to 387.1 mA·h/g, and the capacity retaining rate (S ₂₀) at the 20th cycle grows from 31.3% to 71.7%. Melt-spinning engenders an impactful effect on the electrochemical hydrogen storage performances of the alloys. With the increase in the spinning rate from 0 to 30 m/s, the maximum discharge capacity increases from 30.3 to 135.5 mA·h/g for the Mg₂₀Ni₁₀ alloy, and from 197.2 to 406.5 mA·h/g for the Mg₁₈La₂Ni₁₀ alloy. The capacity retaining rate (S ₂₀) of the Mg₂₀Ni₁₀ alloy at the 20th cycle slightly falls from 36.7% to 27.1%, but it markedly mounts up from 37.3% to 78.3% for the Mg₁₈La₂Ni₁₀ alloy.     

Effects of Si and Ce on the microstructure and hydrogen storage property of Ti_(26.5)Cr_(20)V_(45)Fe_(8.5)Ce_(0.5) alloy

In this paper, the effects of Si and Ce on the microstructure and hydrogen storage property of Ti26.5 Cr20V45Fe8.5Ce0.5 alloy were studied, respectively. First of all, effects of Si on the microstructure and hydrogen storage properties of Ti26.5Cr20(V45Fe8.5)1?xSixCe0.5 (x = 0, 0.5, 1.0, 1.5 and 2.0 at%) alloys were studied by X-ray diffraction, scanning electron microscopy and P-C isotherm measurements. As the Si addition increases, the hydrogen absorption capacities of alloys decrease but the equilibrium pressure increases, due to the formation of Laves phase. Secondly, the effect of Ce on Ti26.5Cr20 (V45Fe8.5)0.98Si2 alloy was studied. It was found that Ce addition is an effective way to eliminate the effect of Si on the hydrogen storage properties of the alloy.     

贮氢材料研究进展

氢是一种清洁的绿色能源,其应用研究受到了广泛的关注。氢能的利用可以保护环境、减少污染、充分发挥能源利用率。本文概述了贮氢材料的种类及其最新的研究进展,介绍了贮氢材料的性能特点,并对贮氢合金、轻质金属-铝氢化物、玻璃微球、碳纳米管、高比表面活性炭、有机液体氢化物等贮氢材料做了进一步的综述。     

气体雾化AB5型贮氢合金微观结构特征及电化学性能

用气体雾化方法可以制备具有CaCu5型六方晶体结构MmNi5-x(CoMnAl)x的球形贮氢合金粉．其贮氢合金表面存在氧化层．气体雾化合金需要较长周期才能充分活化，然而气体雾化合金的循环寿命明显优于机械球磨合金．