材料期刊网

MONTE CARLO SIMULATION STUDY OF SURFACE ELECTRONIC EXCITATION OF NOBLE METALS

H.M. Li , Z.J. Ding , Q.R. Pu

金属学报(英文版)

In this work we present a numerical simulation of REELS-spectrum for noble metals,Au and Ag. The calculation is based on an electron-surface inelastic scattering modelpreviously developed. The differential inelastic cross section is obtained fron an inho-mogeneous electron self-energy in the surface region, which provides full informationof the dependency of the total and differential cross section on the kinetic energy,the distance from the surface and the moving direction of electrons, accommodatingthe formulation to the practical situation in surface electron spectroscopes. A novelMonte Carlo simulation code of electron interaction with a surface incorporating thelocal scattering mean free path has been developed. The comparison of the simulatedREELS-spectra with the experimental measurements shows a remarkable agreement onthe spectrum shape, which then confirms that the present model for electron-surfaceinelastic .scattering is quite reasonable. The simulation has further shown the compo.nent to surface excitation due to the individual scattering processes along trajectorypart, i.e., the loss in vacuum before reflection, the loss in vacuum after reflection andloss in metal events.

关键词: Monte Carlo , null , null , null , null

Effect of Li(3)N additive on the hydrogen storage properties of Li-Mg-N-H system

Journal of Materials Research

The effect of Li(3)N additive on the Li-Mg-N-H system was examined with respect to the reversible dehydrogenation performance. Screening Study with varying Li(3)N additions (5, 10, 20, and 30 mol%) demonstrates that all are effective for improving the hydrogen desorption capacity. Optimally, incorporation of 10 mol% Li(3)N improves the practical capacity from 3.9 wt% to approximately 4.7 wt% hydrogen at 200 degrees C, which drives the dehydrogenation reaction toward completion. Moreover, the capacity enhancement persists well over 10 de-/rehydrogenation cycles. Systematic x-ray diffraction examinations indicate that Li(3)N additive transforms into LiNH(2) and LiH phases and remains during hydrogen cycling. Combined structure/property investigations suggest that the LiNH(2) "seeding" should be responsible for the capacity enhancement, which reduces the kinetic barrier associated with the nucleation of intermediate LiNH(2). In addition, the concurrent incorporation of LiH is effective for mitigating the ammonia release.

关键词: complex hydrides;improvement;mixtures;imides;amide;h-2

V-M(M=Li,Na,K,Sc,Ag)二元系的相图热力学研究

胡标 , 尹明 , 王庆平 , 闵凡飞 , 杜勇

兵器材料科学与工程

基于文献报道的实验数据,采用相图计算(CALPHAD:CALculation of PHAse Diagrams)方法对V-M(M=Li,Na,K,Sc,Ag)5个二元系进行相图热力学研究.通过热力学优化计算获得了一套描述液相、(V)、(Li)、(Na)、(K)、(αSc)、(βSc)和(Ag)相的热力学参数.V-Li、V-Na和V-K体系中的气相视为由组元V、Li、Li2、Na、Na2、K和K2混合的理想气体.与实验相图数据对比表明,获得的热力学参数能够准确地描述实验相平衡数据.

关键词: V-M(M=Li,Na,K,Sc,Ag) , CALPHAD方法 , 相图 , 热力学模型

Li1+xV3-yMyO8(M=Mo,P)高温阴极放电性能的研究

曹笃盟 , 李志友 , 周科朝

稀有金属材料与工程

采用固相反应法制备了Li1+xV3-yMyO8(M=Mo,P;0≤y≤0.4),研究了不同Mo和P含量对Li1+xV3O8相的影响,并首次对其进行了高温阴极放电性能的研究.结果表明:Mo和P掺杂量分别为y≤0.2和y＜0.2时可获得纯Li1+xV3O8相;Mo掺杂使Li1+xV3O8峰值电压提高0.3 V,比容量提高25%,嵌入的Li+量最高可达x=3.8;P掺杂(y≤0.20)对Li1+xV3O8的峰值电压和比容量影响较小.化学嵌锂实验也证实掺杂后的材料具有更快的Li+嵌入速度.

关键词: Li1+xV3O8 , 热电池 , 掺杂 , 比容量

Enhanced Hydrogen Storage Properties of Li-Mg-N-H System Prepared by Reacting Mg(NH(2))(2) with Li(3)N

Journal of Physical Chemistry C

The Li-Mg-N-H system was prepared by reacting magnesium amide [Mg(NH(2))(2)] with lithium nitride (Li(3)N) and investigated with regard to the hydrogen storage properties. Our study shows that the present method is superior to the conventional route in enhancing the reversible dehydrogenation properties. Through optimizing the Li(3)N:Mg(NH(2))(2) ratio in the starting materials, the reversible capacity of U-Mg-N-H system increases to 4.9 wt %, 18% higher than that typically obtained from the Mg(NH(2))(2) + 2LiH mixture at 200 degrees C. Furthermore, increasing the Li(3)N:Mg(NH(2))(2) ratio is effective for mitigating the ammonia release from thus-prepared samples. Combined property/structure investigations indicate that the obtained enhancements should be ascribed to the effects of LiNH(2) and LiH that were in situ generated from the excess Li(3)N. LiNH(2) may promote the dehydrogenation reaction via seeding the reaction intermediate. The concurrently generated LiH acts as an effective ammonia trapping agent. These findings highlight the potential of "intermediate seeding" as a strategy to enhance the reversible hydrogen storage properties of metal-N-H systems.

关键词: complex hydrides;ultrafast reaction;amide;improvement;desorption;linh2;destabilization;mechanism;mixtures;imides

Li-Mg-N-H储氢材料储氢性能测试方法研究

裴增文 , 刘晓鹏 , 黄倬 , 李志念 , 王树茂 , 蒋利军

稀有金属 doi:10.3969/j.issn.0258-7076.2010.04.013

采用等容法研究了机械球磨工艺制备的Li-Mg-N-H材料储氧性能,结果发现,在室温下采用氦气对样品室体积进行标定时,由于Li-Mg-N-H材料对氦气有一定量的物理吸附,造成准确Li-Mg-N-H材料样品体积标定误差,进而造成Li-Mg-N-H储氢材料在503 K下放氢容量随压力的降低而增加异常变化.为准确标定样品体积,通过对Li-Mg-N-H材料室温氮气吸附容量测定,并采用迭代计算方法获得准确的储氢材料样品体积,进而测定Li-Mg-N-H储氢材料503 K下放氢PCT曲线,其表现为放氢容量随压力降低而减小的正常变化规律.Li-Mg-N-H储氢材料503 K,9.6 MPa氢压下的最大储氢容量为4.81%(质量分数),放氢过程表现为单一放氢平台特性.

关键词: 轻质储氢材料 , Li-Mg-N-H , 储氢性能 , 等容测试方法

First-principles study on influence of alloying element substitution on dehydrogenation ability of Li(4) BN(3) H(10) hydrogen storage materials

Acta Physica Sinica

A first-principles plane-wave pseudopotential method based on the density functional theory is used to investigate the dehydrogenation properties and the influence mechanism of Li(4)BN(3)H(10) hydrogen storage materials. The binding energy, the density of states and the Mulliken overlap population are calculated. The results show that the binding energy of crystal has no direct correlation with the dehydrogenation ability of (LiM)(4)BN(3)H(10)(M = Ni, Ti, Al, Mg). The width of band gap and the energy level of impurity are key factors to affect the dehydrogenation properties of (LiM)(4)BN(3)H(10) hydrogen storage materials: the wider the energy gap is, the more strongly the electron is bound to the bond, the more difficulty the bond breaks, and the higher wile the dehydrogenation temperature be. Alloying introduces the impurity energy level in band gap, which leads the Fermi level to enter into the conduction band and the bond to be weakened, thereby resulting in the improvement of the dehydrogenation properties of Li(4)BN(3)H(10). It is found from the charge population analysis that the bond strengths of N-H and B-H are weakened by alloying, which improves the dehydrogenation properties of Li(4)BN(3)H(10).

关键词: hydrogen storage materials;first-principles calculation;element;substitution;dehydrogenation;linh2

Enhanced H-storage property in Li-Co-N-H system by promoting ion migration

Journal of Alloys and Compounds

Motivated by the ion migration mechanism proposed by David et al. [J. Am. Chem. Soc. 129 (2007) 1594-1601], we mechanically mill the Li3N/Co powder mixture to obtain defective Li3N-type structure with enhanced Li+ mobility. Compared with Li3N the hydrogen storage property of such defective phase is markedly improved, presumably due to the ion-migration-enhancing effect from the incorporation of Co and Fe (from milling utensils). During subsequent cycling, however, this effect cannot persist due to the precipitation of Co-Fe alloy upon hydrogenation. The close correlation between Co-Fe incorporation/precipitation and property variation of Li3N hydrogen storage material provides a preliminary evidence to support the ion migration mechanism. (C) 2007 Elsevier B.V. All rights reserved.

关键词: Hydrogen absorbing materials;Nitride materials;hydrogen-storage;lithium amide;mechanism;nitride;batteries;mixtures;hydride;imides;linh2;anode

Oxygen reduction mechanism on copper in a 0.5 M H(2)SO(4)

Electrochimica Acta

The mechanism of the oxygen reduction reaction (ORR) in a naturally aerated stagnant 0.5 M H(2)SO(4) Was studied using electrochemical methods. The cathodic polarization curve showed three different regions; electrochernical impedance spectroscopy (EIS) measurement was used accordingly. The EIS data were analyzed, and the mechanism for the ORR was proposed consequently. The three regions include a limiting current density region with the main transfer of 4e(-) controlled by diffusion (-0.50V < E < -0.40V), a combined kinetic-diffusion region (-0.40V

关键词: Oxygen reduction;Hump phenomenon;Chemical redox;Copper;Electrochemical impedance spectroscopy;sulfuric-acid electrolyte;anodic-dissolution;sulfate-solutions;corrosion;behavior;adsorption;chloride;cu(111);alloy;model

Local structures of the tetragonal Gd3+-V-M and Gd3+-Li+ centers in perovskite fluorides

Radiation Effects and Defects in Solids

The zero-field splittings b(2)(o) of the tetragonal Gd3+-V-M and Gd3+-Li+ centers for Gd3+ ions in fluoroperovskite crystals have been studied on the basis of the superposition model in which the value of t(2) (b) over bar(2) is Obtained from the stress-dependence of EPR spectra for RbCaF3:Gd3+ crystal. From the studies, the local structures of both tetragonal centers in fluoroperovskite crystals are obtained and the results are discussed.

关键词: electron paramagnetic resonance;local crystalline structure;superposition model;Gd3+;fluoroperovskite;electron-paramagnetic-res;crystals;cr-3+-li+;spectra;epr