SiO2包覆对含微量CO氢环境中LaNi4.25Al0.75吸氢动力学性能的影响

采用气相二氧化硅法制备了LaNi4.25Al0.75/SiO2复合材料,研究了该复合材料表面形貌以及氢中微量CO对LaNi4.25Al0.75合金及LaNi4.25Al0.75/SiO2复合材料吸氢动力学性能的影响。结果表明：合金被毒化后,在表面生成含NiO、La(OH)3、La2O3、Al(OH)3的氧化层,并且吸附大量CO,导致合金的吸氢量减少,动力学变慢。表面包覆SiO2可显著改善合金抗毒化性能     

SiO2/Al复合材料的制备及性能研究

采用液态机械搅拌法制备了SiO2/Al复合材料.对复合材料中颗粒的分布、界面反应及复合材料物理力学性能进行了分析测试.结果表明,当复合材料颗粒含量较低时分布比较均匀;复合材料界面反应产物主要有Mg 2Si,MgAl2O4,MgO相,Si含量较少;热导率、热膨胀系数均随SiO2颗粒含量增加而减少;布氏硬度随SiO2颗粒含量增大而增大;SiO2颗粒含量较少(w(SiO2)＜6%)时,复合材料的抗压强度随SiO2颗粒含量增大而增大,但含量继续增加抗压强度反而降低.     

热处理温度对LaNi3.8Al1Mn0.2合金储氢性能的影响

对热处理(1173K, 1223K, 1273K, 1323K)前后LaNi3.8Al1.0Mn0.2合金的研究表明,热处理前后合金均由一个主相,三种第二相组成。热处理后第二相后变小,分布更加弥散,第二相中LaNi2变为LaNi相,晶胞参数和晶胞体积增加,活化性能变差,但吸放氢平台压降低,吸放氢平台的斜率和滞后变小,合金的吸氢速度显著变快,吸放氢焓变和吉布斯自由能的绝对值增大,而吸氢量未见明显变化。随着热处理温度的升高,晶胞参数和晶胞体积先增大后减小,吸放氢平台压先降低后升高,斜率先增大后减小,滞后先减小后增大,而焓变和自由能的绝对值先增加后减小,在1223K分别达到最大和最小值,而热处理温度的升高使活化性能和动力学性能略有提升。     

Photoluminescence properties of ZnSe/SiO2 composite thin films prepared by sol-gel method

ZnSe/SiO2 composite thin films was prepared by sol-gel method. XRD results indicate the phase structure of ZnSe particles embedded in ZnSe/SiO2 composite thin films is sphalerite （cubic ZnS）. Spectroscopic ellipsometers were used to investigated the dependences of ellipsometric angle with wavelength of ZnSe/SiO2 composite thin films. The optical constant, thickness, porosity and the concentration of ZnSe of ZnSe/SiO2 thin composite films were fitted according to Maxwell-Garnett effective medium theory. The thickness of ZnSe/SiO2 composite thin thin films was also measured through surface profile. The photoluminescence properties of ZnSe/SiO2 thin composite thin films was investigated through fluorescence spectrometer. The photoluminescence results show that the emission peak at 487 nm （2.5 eV） is excited at 395 nm corresponds to the band-to-band emission of sphalerite ZnSe crystal（2.58 eV）. The strength free exciton emission and other emission peaks correlating to ZnSe lattice defect were also observed.     

SiO2与液态Al反应生成Al2O3/Al复合材料的研究

采用SiO2粉与液态Al反应制备Al2O3／Al复合材料，讨论了SiO2的加入量、反应温度、反应时间对反应速度的影响，分析了不同反应温度和保温时间下生成复合材料的微观结构。试验证明：当SiO2含量较低时，SiO2与Al发生完全反应，形成均匀Al2O3／Al复合层；当ω(SiO2)达一定量时，反应速度反而降低；保温时间为6～8h，反应速度最快，之后变慢。     

铝合金表面SiO2陶瓷膜的研究

为了提高铝合金的表面硬度，增加其耐磨性，采用溶胶．凝胶法在铝合金表面制备了SiO2陶瓷表面膜，研究了乙醇、水、pH值和甲酰胺等相关工艺因素对溶胶性能及SiO2陶瓷表面膜的影响，以及SiO2陶瓷表面膜对铝合金表面硬度的改善情况。结果表明，通过控制相关工艺因素，可以在铝合金表面获得光滑平整的SiO2陶瓷表面膜，陶瓷表面膜能明显提高铝合金的表面硬度，浸涂7层SiO2陶瓷表面膜后，铝合金的表面硬度提高76％。     

LiBH4／Mg复合氢化物的储氢性能研究

通过球磨LiBHdMg，使得镁的吸放氢性能得到明显改善。活化结果显示，在氩气气氛下，球磨1h的LiBHdMg混合物经250℃，60min处理后的吸氢量可以达到6．7％（质量分数，下同）。200℃，80min处理后的吸氢量可以达到3．0％。而纯镁粉在相同条件下几乎不吸氢。PCT结果显示，LiBH4也明显改善镁氢化后的放氢性能。     

La1-xYxNi4.8Al0.2合金的储氢性能研究

本文系统地研究了Y元素对La1-xYxNi4.8Al0.2 (x=0.6,0.7,0.8)储氢合金的晶体结构、吸放氢热力学、动力学和抗粉化性能的影响.研究结果表明,合金为CaCu5型六方结构,随着Y含量的增加,晶格参数a和晶胞体积v减小,而c几乎不变,c/a线性增大.随着Y含量的增加,合金吸放氢平台压显著升高;吸氢量略有减少;吸放氢平台斜率变小;滞后系数先减小后略增大,并与XRD(111)峰的半高宽FWHM值的变化有着很好的对应关系;抗粉化性能略有提高.当Y含量x=0.7时,合金的吸放氢动力学综合性能最好.     

SiO2-TiO2-ZrO2干凝胶制备工艺和性能

采用正硅酸乙酯(TEOS)、氧氯化锆(ZrOCl2·8H2O)和钛酸丁酯(TBT)为前躯体,以无水乙醇(EtOH)为溶剂通过溶胶-凝胶法制备以SiO2作为干凝胶主组分的SiO2-TiO2-ZrO2干凝胶.研究了多元干凝胶的溶胶-凝胶法制备技术、干凝胶改性技术以及各种制备工艺参数的影响规律.当原料比m(氧氯化锆)∶m(钛酸丁酯)∶m(氨水)∶m(TEOS)∶m(EtOH)=1∶2.7∶5.0∶16.7∶106.7时,经过水解、老化及溶剂替换后,制得气孔率约85％,比表面积190 ～210 m2/g,孔径6～ 30 nm,粒子直径小于20 nm,导热系数可达到0.0857 W·m-1 ·K-1的SiO2-TiO2-ZrO2干凝胶.     

碳纤维表面SiO2涂层的制备及其在镁基复合材料中的应用

利用Sol-Gel方法,通过优化溶胶的配置、纤维提拉过程和干燥烧结等工艺过程,在碳纤维表面制备出均匀的、无裂纹的SiO2涂层.采用SEM、XPS和TEM表征了碳纤维表面SiO2涂层的结构、形貌、元素分布以及涂层碳纤维/镁基体的界面结构.结果表明,涂覆SiO2的碳纤维,抗氧化能力提高,拉伸性能略有降低,但与镁基体复合后其拉伸强度降低了20%.SiO2涂层改善了Mg对碳纤维的润湿能力,有效地促进了熔融Mg液对碳纤维的浸渗.     

Structural stability of single-layered LaNi4.25Al0.75 film and its electrochemical hydrogen-storage properties

AB5-based hydrogen storage thin fdms （LaNi4.25Al0.75）, deposited on Cu substrate by dc magnetron sputtering were investigated in this study. X-ray diffraction （XRD） revealed that the microstructure of the layer was in crystal form. SEM and AFM analyses proved that the film appeared to be rather rough with numerous randomly sized pores of approximately 15-40 in nm diameter. Structural stability of the film was examined by the combined analyses of DSC, XRD, and SEM, which indicated that this film maintained its structural stability below 500 K or so, and a network structure was observed on the film after being heated at 700 K for 30 min. Electrochemical hydrogen-storage properties of the films were investigated by simulated battery tests. It was found that single-layered LaNi4.25A10.75 film exhibited electrochemical hydrogen-storage properties similar to typical AB5 alloys in bulk, and the maximum discharge capacity of the film was about 220 mAh/g. After 20 charge/discharge cycles, small needle-shaped aluminium oxide was formed on some fractions of the film surface.     

表面Pd膜对LaNi_(4.25)Al_(0.75)合金贮氢性能的影响

为改善LaNi4.25Al0.75贮氢合金表面抵抗杂质气体毒化的能力,采用化学镀对粒径d为150~300μm的LaNi4.25Al0.75颗粒进行了表面金属Pd的包覆。通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)对化学镀前后LaNi4.25Al0.75合金颗粒的表面形貌及结构进行表征分析;采用容量法测试材料的贮氢性能。结果表明:化学镀在LaNi4.25Al0.75颗粒表面沉积了一层晶体Pd单质,膜层均匀且有一定的致密性。表面金属Pd层能够使LaNi4.25Al0.75颗粒在含杂质(O2和N2)氢气中的贮氢容量的衰减幅度由1.928%降至0.086%,有效提升了其抵抗O2和N2毒化的能力。     

Hydrogen storage properties of melt-spun LaNi4.25Al0.75

Rapidly solidified LaNi_4.25Al_0.75 alloy was prepared by melt spinning and its hydrogen storage properties were examined. The hydrogen storage capacities and the equilibrium pressures of the unannealed melt-spun (UMS) LaNi_4.25Al_0.75 alloy were found to be nearly identical to those of the annealed induction-melt (AIM) alloy. However, the resistance to pulverization was greatly improved and the hysteresis was markedly decreased for the UMS alloy, while its activation became rather difficult.     

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.     

LaNi4.75Al0.25储氢材料的密度泛函理论研究

在全电子水平上，基于广义梯度近似（GGA）密度泛函和全势能线性缀加平面波方法（FLAPW），研究了LaNi4.75Al0.25的晶体结构。采用GGA Perdew96交换相关泛函，计算给出了LaNi4.75Al0.25的晶胞参数为a=b=0．5033nm、c=0．4018nm、a／c=1．252，Al原子最可能占据的3g格位的等效位置（0．75，0，0．5），计算还给出了合金的能带结构、态密度（DOS）和电荷密度图，计算结果与实验值符合得相当好。     

二氧化硅溶胶包裹镧镍铝合金的制备

采用气相二氧化硅处理镧镍铝合金,研究二氧化硅溶胶包裹镧镍铝合金的制备方法。对干燥后的样品进行了SEM分析,研究了水含量、镧镍铝合金含量和合金粒度、干燥工艺对样品吸氢性能的影响。结果发现,绝大多数镧镍铝合金颗粒都能被包裹在二氧化硅胶体内;溶胶的粘度随着水含量的增加、时间的延长逐渐降低;水和二氧化硅的含量控制在8:1时,样品的吸氢速度较快;镧镍铝合金含量越低,样品中单位质量的金属吸氢量越高;合金粒度越小,合金颗粒越容易被胶体包裹住,样品的吸氢性能也相对越好;另外,样品干燥过程中并不一定需要有惰性气体保护。在0.2 MPa氢压下,样品的吸氢量和吸氢速度都明显优于LaNi4.8Al0.2合金     

Ni/LaNi5多孔复合电极的制备及其析氢电催化性能

先电沉积Ni-Zn合金镀层,然后用浓碱将镀层中的锌脱溶,得到多孔镍,最后采用复合电沉积将LaNi5镶嵌到多孔镍表面,制备成Ni/LaNi5多孔复合电极。采用稳态极化曲线和交流阻抗谱对电极的电催化析氢性能进行了评价,并运用恒电位间歇电解和长时间电解,开路电位等研究了电极的电析氢稳定性。结果表明:Ni/LaNi5多孔复合电极的析氢表观交换电流密度分别是镍和多孔镍的172倍和26倍;多孔复合电极中的LaNi5具有稳定电极的作用,该电极比多孔镍具有更优异的抗断电性能。     

LaNi3.70Al0.75Mn0.55合金吸氚特性

通过分析LaNi_3.70Al_0.75Mn_0.55合金材料在室温下定容吸氚压力随时间的变化规律,研究LaNi_3.70Al_0.75Mn_0.55合金吸氚的反应机制。结果表明,氚压力在材料吸氚初始阶段下降迅速,在15s内吸氚T/M比(每克金属吸氚量)可达到1.5std.cm³/g,吸氚速率最快能达到0.28std.cm3·g^-1·s^-1,最大吸氚速率发生在α+β相区。氚在合金表面的解离和化学吸附为吸氚初期的控速步骤。当T/M>15 std.cm3/g时,反应产生β相变,形成氚化物,形核长大为吸氚过程控速步骤。     

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.