真空快淬技术制备贮氢合金的新近进展

本文介绍了应用真空快淬技术制备贮氢合金。应用真空快淬技术可使合金在极大的过冷度下凝固，经过真空快淬处理后贮氢合金获得具有微晶、纳米晶、非晶特殊微观结构，因而表现出良好的电化学性能。介绍了真空快淬技术在稀土镍系AB5型，AB2型Laves相，稀土镁基贮氢合金等制备中的应用现状，评价了真空快淬技术在制备新型贮氢合金中的作用。     

稀土系贮氢合金热处理的研究与进展

AB5型稀土系贮氢合金因其具有良好的性能而得到广泛应用。本文综述了热处理对AB5型稀土系贮氢合金微观结构以及电化学性能的影响,指出通过适当的热处理工艺可以获得良好的电化学性能。     

金属氢化物氢压缩机用AB2型Ti- Mn基储氢合金研究

制备了AB2型Laves相Ti- Zr- Mn- Cr- V- Fe系列氢压缩材料,对于V- Fe、Mn/Cr比值和Zr含量对合金吸放氢平台特性和热力学性能的影响进行了研究,优化出具有优异综合储氢性能的氢压缩材料Ti0.9Zr0.1Mn1.4Cr0.35V0.2Fe0.05合金.该合金具有较低的吸放氢平台压力、较小的压...     

AB_3型La-Mg-Ni系稀土贮氢合金电极合金结构和贮氢性能

用感应熔炼的方法制备了AB_3型La-Mg-Ni系稀土贮氰电极合金,采用X射线衍射、Sievert型测试仪、三电极测试体系研究了合金的相结构、吸氢性能、电化学性能.X射线衍射分析结果表明,AB_3型La-Mg-Ni系稀土贮氢电极合金均南(La,Mg)Ni,相、(La,Mg)_2Ni_7相及少量杂质相组成,为多相结构;贮氢性能实验研究表明,具有PuNi_3结构的LaNi_3,型合金的吸氧量高于具有CaCu_5结构的LaNi_5型合金.     

加V低Co-AB5型贮氢合金研究

对AB5型稀土系贮氢合金进行多元合金化降钴研究，在贮氢合金Ml（NiCoMnAl）4.5（CuFeCrZn）0.5-xVx的基础上，依次增加V（x=0．02，0．05，0．08）元素含量替代Co的方法制备加V低Co-AB，型贮氢合金，并对其放电容量、循环稳定性以及微观结构进行了测试和分析。结果表明，可以获得综合电化学性能良好的加V低Co贮氢合金。但V的加入量应严格控制，在x=0．02的加V低Co贮氢合金具有较佳的综合电化学性能。     

Structures and hydrogen storage properties of RE-Mg-Ni-Mn-based AB_2-type alloys prepared by casting and melt spinning

To ameliorate the electrochemical hydrogen storage properties of RE-Mg-Ni-Mn-based AB_2-type electrode alloys,La element was partially substituted by Ce,and La_(1-x)Ce_xMgNi_(3.5)Mn_(0.5)(x=0,0.1,0.2,0.3,0.4)alloys were fabricated by casting and melt spinning.The effects of Ce content on structures and electrochemical hydrogen storage properties of prepared alloys were studied in detail.Results show that the experimental alloys consist of LaMgNi_4 and LaNi_5 phases.The variation of Ce content,instead of changing phase composition,results in an obvious phase abundance change in the alloys,namely the amount of LaMgNi_4 and LaNi_5 phases,respectively,increases and decreases with Ce content growing.Moreover,the partial substitution of Ce for La leads to that the lattice keeps constant,cell volumes clearly decreases and the alloy grains are markedly refined.The electrochemical measurements reveal that the as-cast and as-spun alloys obtain the maximum discharge capacities at the first cycling without any activation needed.With Ce content increasing,the discharge capacity of as-cast alloys visibly decreases.By contrast,the as-spun alloys have the maximum discharge capacity value.The substitution of Ce for La dramatically promotes the cycle stability.Moreover,the electrochemical kinetic performances of as-cast and asspun alloys first increase and then decrease with Ce content increasing.     

镁基储氢合金的最新研究进展

镁基合金是一类重要的储氢材料。本文综述了Mg2Ni系合金、稀土-镁-镍、镁-稀土等3类含镁储氢合金的最新研究进展,探讨了合金化机理,即合金化元素、原子半径、相结构对含镁基储氢合金性能的影响规律。     

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％。     

Study on Hydrogen in Mixed Gas Separated by Rare Earth Hydrogen Storage Alloys

采用中频感应炉在氩气保护下制备稀土镍系AB5型贮氢合金和La-Mg-Ni系AB3型贮氢合金。利用H2、N2和CH4配制的混合气体来模拟工业尾气,对利用稀土贮氢合金分离混合气体中氢气的纯度、合金抗杂质气体毒化及抗粉化性能进行研究。结果表明,稀土镍系AB5型合金由CaCu5型结构组成,AB3型La-Mg-Ni系合金为多相结构,由(La,Mg)Ni3、LaNi5以及LaNi2型相组成。在分离混合气体中氢气时,贮氢合金均受到杂质气体的毒化,导致吸氢速率降低,吸氢量减少。La-Mg-Ni系合金的抗粉化性能好于LaNi5及其多元化合金。综合考虑分离氢气的纯度、合金的抗毒化及抗粉化性能,认为LaNi3.7Mn0.4Al0.3Fe0.4Co0.2合金分离氢气的效果较好,氢气纯度可以达到90.7%。     

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.     

掺Pd改性纳米晶Mg2Ni吸放氢氘特性研究

采用机械合金化法制备了Mg2Ni-1．0％Pd（质量分数，下同）合金粉末，用XRD及AFM等分析表征了球磨20h后粉末的相结构和微观形貌，测定了Mg2Ni-1．0％Pd合金吸放氢氘的P-C-T曲线和动力学曲线。结果表明，机械合金化制备的Mg2Ni-1．0％Pd合金粉末粒度在10nm～50nm之间；同熔炼法制备的Mg2Ni合金相比，纳米Mg2Ni-1．0%Pd合金吸氢时的焓变值减小，放氢时焓变值增大，可逆贮氢容量为1．06（H／M,原子比，下同）；与吸放氢相比，在相同温度下合金吸放氘的坪台压升高，焓变值减小，具有显著的同位素效应。纳米Mg2Ni-1．0％Pd合金的吸氢速率和吸氘速率与温度的关系在573K附近发生变化。     

含Sc镁镍储氢合金的电化学性能

采用机械合金化方法制备Mg1-xScxNi(x=0,0.01)系列储氢合金.XRD结构分析表明,该系列合金为非晶态合金.XPS分析结果表明,加入微量Sc可以有效地抑制合金表面的氧化程度和提高合金表面Ni与Mg的原子个数比.电化学测试结果表明,微量Sc改善了合金电极的电化学性能,Mg0.99Sc0.01Ni合金电极的放电容量、容量保持率S10、高倍率放电能力HRD200、交换电流密度I0和极限电流密度,IL分别较MgNi合金电极提高10.5%、14.7%、30.4%、202.7%和77.8%.     

Zr基和Ti基块体非晶合金的电化学腐蚀性能(英文)

用电化学方法研究Ti基和Zr基非晶合金及与非晶成分相同的Zr基晶态合金在1mol/LH2SO4和3.5%NaCl溶液中的腐蚀行为。极化曲线测试结果表明:在H2SO4溶液中,Zr基非晶和晶态合金自腐蚀电位比Ti基非晶合金的低;在NaCl溶液中,Zr基晶态合金的自腐蚀电位最低,而且在腐蚀过程中没有发生钝化,然而非晶合金都表现出钝化特性。交流阻抗测试结果表明:在NaCl溶液中非晶合金比晶态合金表现出更好的耐腐蚀性能,但是在H2SO4溶液中并没看到它们之间有明显的区别。表面形貌分析表明:在NaCl溶液中,这2种非晶合金都发生点蚀,而在H2SO4溶液中所有试验合金都表现出类似的特征,试样表面基本保持平整,只是在腐蚀表面的局部区域有一些裂纹出现。     

Numerical simulation of hydrogen desorption from high-density metal hydride hydrogen storage vessels

Metal hydride (MH) alloys are a promising type of material in hydrogen storage applications, allowing for low-pressure, high-density storage. However, while many studies are being performed on enhancing the hydrogen storage properties of such alloys, there has been little research on large-scale storage vessels which make use of the alloys. In particular, large-scale, high-density storage devices must make allowances for the temperature variations caused by the heat of reaction between hydrogen and MH alloys, which may impact the storage characteristics. In this study, we propose a numerical model for the design and evaluation of hydrogen storage devices using MH alloys. Hydrogen desorption reaction behavior for an alloy is observed in terms of temperature and reaction rate. This behavioral correlation is used as the basis for a comprehensive simulation model of the alloy system. Calculated results are found to be in good agreement with experimentally measured data, indicating that the model may be applied to multiple system geometries, scales, and alloy compositions.     

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%.     

低钴储氢合金Ml0．9Mg0．1Ni3．4Co0．3Al0．3电化学性能研究

为了降低AB5犁储氢合金的成本，对低钴的Ml0．9Mg0．1Ni3．4Co0．3Al0．3合金的组织结构和性能进行了研究，并与工业储氢合金MmNi3.55Co0.75Mn0.4Al0.3进行了对比。实验结果表明：此低钴合金是由LaNi5主相和LaNi3第二相构成。它们的储氢晕（ω,％）分别为1．36％和1．37％，最大放电容量分别为320mAh／g和324mAh／g，循环稳定性为：300次充放电循环后，2种合金剩余容晕都是88％。但Ml0．9Mg0．1Ni3．4Co0．3Al0．3的高倍率放电性能明显优于MmNi3．55Co0．75Mn0．4Al0.3合金。主要原因是由于LaNi3第二相的乍成不仪提高了合金颗粒表面的电化学催化活性，而且提高了结构韧性从而抵消了低钴合金颗粒粉化的不利影响。     

Zr在Mg2Ni储氢合金中的作用

采用感应熔炼法制备了Mg2Ni1-xZrx(x=0、0.2、0.4)合金,研究了Zr的添加对Mg系储氢合金储氢性能的影响。对合金的成分和微观组织进行分析,结果表明,Zr较难融入到合金,但是Zr能使得合金晶粒得到细化,且合金中都有Mg2Ni相的形成,有利于吸氢反应的进行。利用PCT测试仪测定了合金的储氢性能,结果表明:添加Zr元素的添加能有效降低Mg2Ni的吸放氢温度,并能有效提高提高合金的吸氢量,最高吸氢量达到4.91wt%。     

Nb、Ta等元素对Zr基大块非晶非晶形成能力及耐腐蚀性影响机理研究

  用计算机编程构造了Zr基非晶合金包含二十面体原子团簇的Zr₂Ni晶体相.用Zr₂Ni晶体相中以Ni原子为中心的二十面体原子团簇模拟Zr基非晶中二十面体团簇.应用实空间的递归方法计算了合金元素取代二十面体原子团簇中心和顶角位置原子时的局域态密度、二十面体原子团簇中中心Ni原子与其近邻合金元素Nb、Ta、Ti、V的总键级积分及团簇的费米能级.结果表明,Nb、Ta、Ti和V取代Zr原子后使其与Ni的键级积分有所降低,使合金的非晶形成能力下降,但Nb、Ta对合金的非晶形成能力影响不大;Nb、V取代Zr使费米能级升高,可使Zr基非晶容易钝化,提高耐蚀性;Ta对Zr基非晶的耐蚀性影响不大.而Ti使Zr基非晶的钝化能力下降.综合合金元素对非晶形成能力和耐腐蚀性的影响,Nb是最有益的合金元素,即在Zr基非晶中,通过加入少量的Nb元素,可以制备出具有较高耐腐蚀性的大块非晶.     

Environmental properties of Zr-based metallic glasses and nanocrystalline alloys

Zr-Cu-Ni-Al belongs to the best glass forming systems known; these glasses are suitable as precursor material for nanocrystalline alloys. For an application as hydrogen storage materials for example it is of great interest to know more about these metastable materials in regard to their environmental properties. Corrosion as studied by a salt spray test or anodic polarization in aqueous solutions exhibit a rather high sensitivity with no significant differences between the amorphous and nanocrystalline state. Hydrogen charging was performed electrochemically in a glycerine-phosphoric acid electrolyte. In Zr-Cu-Ni-Al alloys absorption kinetics and storage capacity were found to be very similar for the amorphous and the nanocrystalline phase. In the nanocrystalline alloy consisting mainly of a fcc (big cube) phase with a NiTi₂ type structure a hydrogen induced amorphization was observed. Oxidation of metastable Zr-based materials in air was studied below the glass transition temperature at 360°C by thermogravimetry. Oxidation resistance was found to improve very significantly from the amorphous to the nanocrystalline microstructure. The scales formed on both materials consist mainly of columnar ZrO₂ with diameter in the nanometer range; Probably including the other metals as a nanocrystalline solid solution.     

Enhanced Electrochemical Hydrogen Storage Characteristics of Nanocrystalline and Amorphous Mg20Ni10-xCox (x=0-4) Alloys by Melt Spinning

In order to improve the electrochemical hydrogen storage performances of the Mg2Ni-type alloys, Ni in the alloy was partially substituted by element Co. The nanocrystalline and amorphous Mg20Ni10-xCox (x=0, 1, 2, 3, 4) alloys were prepared by melt-spinning technology. The structures of the as-cast and spun alloys were studied by XRD, SEM and HRTEM. The electrochemical hydrogen storage characteristics of the alloys were measured. The results show that the substitution of Co for Ni leads to the formation of secondary phase MgCo2 without altering the major phase of Mg2Ni. No amorphous phase is detected in the as-spun alloy (x=0), whereas the as-spun alloy (x=4) holds a nanocrystalline and amorphous structure, confirming that the substitution of Co for Ni significantly increases the glass forming ability of the Mg2Ni-type alloy. The substitution of Co for Ni significantly improves the electrochemical hydrogen storage performances of the alloys, including the discharge capacity and the cycle stability, for which the increased glass forming ability by Co substitution is mainly responsible