Si掺杂过渡元素Sc、Ti、V、Cr电子结构研究

文章采用第一性原理的平面波赝势方法,对单晶Si掺杂4种过渡元素的体系从晶格参数、电子结构以及光学性质等方面进行了理论计算与研究。计算结果表明,在4种掺杂元素中,掺杂Cr元素的晶格参数、晶胞体积反而变小,晶胞能最低,体系也最稳定。从体系的电子结构分析发现,在单晶Si中掺杂这4种过渡元素时,掺杂Cr元素的体系杂化最为剧烈,吸收峰位于费米面以上的2.42～2.80eV区域,是由Si的2p电子与Cr的3d轨道作用所致,在该区域的波长为443～513nm,位于可见光区,同时掺杂Cr的体系最稳定。     

关于过渡元素划分方法的讨论

目前,国内外教科书中对过渡元素的划分方法有多种方式,不尽统一,本文通过对各种划分过渡元素的方法进行分析,说明哪些元素是过渡元素更为合理.     

在V、Cr、Fe、Co体心晶格中的氢原子

本文主要报告了氢原子在bcc(体心立方晶体)型的过渡金属V、Cr、Fe、Co原子簇中结合能的EHMO(推广的Hückel分子轨道理论)计算结果。计算中对Hückel参数K进行了优选,使之更接近于纯金属结合能的观测值。结果表明,在原子簇中氢原子处于歪曲的四面体环境比歪曲的八面体位置更为稳定,邻近的晶格空穴能增加氢原子的稳定性。发现在计算的氢原子结合能与d电子排斥势之间存在着定量的反比关系。     

Fe,Cr及Fe（Cr ）合金磁矩的价电子结构分析

给出了确定单质或二元固溶体原子状态的简单快捷方法,应用该方法可清楚地给出固体中化学键网的分布、键强有关固体的其它特性,如熔点、电导率、磁矩、结合能、强度、韧性等,作为例子,建立了α－Fe,α-Cr和不同Cr含量F(Cr）合金的价电子结构,并对晶格常数和磁矩的实验结果给出了满意的价电子结构分析。     

氢元素在镍氧化物超导体中的重要作用

氢(H)是宇宙中最轻的元素,对大多数最先进的表征技术不敏感,因此很难确定其在材料中的存在和分布.但H元素就像一把“隐形的钥匙”,在材料科学中开启着不同寻常的物理性质. 2019年,无限层结构镍氧化物超导材料(镍基超导)的发现,激励了研究人员寻求更多类似于铜氧化物的新型高温超导材料,以及探究高温超导机理中晶体结构和电子结构的关联.目前,镍氧化物超导体主要通过金属氢化物的拓扑还原制得,随之而来的问题是:在镍基超导中CaH₂辅助的拓扑还原是否会在薄膜中引入“额外”的H元素,并影响其超导态?本文着重回顾了H元素对材料物理性能的影响规律,重点介绍了近年来镍氧化物中H存在的痕迹、H元素在材料内部的原子占据位置,详细分析了H元素对镍基材料超导电性的影响机制,并对今后该领域的研究方向和重点展开了开放性讨论.     

元素性质参数在超导研究中的影响

本文通过分析在超导电性研究中所采用的元素性质参数的影响和所得出的结果。证明微观结构决定宏观性质的规律同样适用于超导电性的研究。进一步研究元素性质参数的实质,揭示出元素的电子构型决定元素的性质,进而决定材料的超导电性性质之间的连锁关系。这对于制备新的超导材料,探索超导机制都是有意义的。     

元素录井技术在海陆过渡相页岩气水平井地质导向中的应用

河南省页岩气资源主要发育于上古生界海陆过渡相沉积中,海陆过渡相页岩气层系具有多岩性频繁互层、单层厚度小、纵向变化快的特点,加上局部地区微幅构造发育,使得水平井地质导向中小层识别和水平段钻头方向的判断难度很大。为此,利用研究区优质页岩气层段的X射线荧光元素录井数据,通过统计分析对目的层各小层进行精细刻画,首次提出利用Si、Al、Na、Fe、S、K、Mn和Ti元素含量的变化关系分别建立砂岩、煤岩和泥岩元素交会图版,并利用Ba、Ti、Ca、S和Sr元素组合与深度的关系建立随钻元素定量模型。根据元素交会图版进行目的层小层识别,为水平井入窗提供准确依据;在水平段利用随钻元素定量模型判断钻头穿行方向。该技术在通许隆起中部中深层页岩气水平井钻井过程中进行了现场应用,取得了较好的效果。     

Crystal structure and hydrogen storage properties of(La,Ce)Ni_(5-x)M_x(M = Al,Fe, or Co) alloys

The effects of partial substitution of La by Ce and Ni by Al, Fe, or Co in LaNi_5-based alloys on hydrogen storage performance were systematically studied. All samples were prepared using vacuum arc melting in an argon atmosphere. The results showed that for LaNi_(5-x)M_x(M = Al, Fe, or Co) alloys, the lattice constants and unit cell volumes increased with an increasing amount of Al and Fe. On the other hand, these parameters decreased upon partial substitution of La by Ce. In addition, the lattice constant remained almost constant in the La_(0.6)Ce_(0.4)Ni_(5–x)Cox alloys regardless of the value of x(x = 0.3, 0.6, or 0.9), as Ce might enhance the homogeneity of the CaCu_5-type phase in Co-containing alloys. The hydrogen storage properties of the alloys were investigated using pressure, composition, and temperature isotherms. The experimental results showed that the plateau pressure decreased with an increasing content of Al, Fe, or Co, but it increased with Ce addition. Furthermore, the plateau pressures of all Co-containing alloys were almost identical upon substitution with Ce. Finally, the enthalpy(ΔH) and entropy(ΔS) values for all alloys were calculated using van't Hoff plots. The relationship between the lattice parameters and enthalpy changes for hydrogenation will be discussed.     

La-Mg-Ni/Co储氢合金中的相结构

应用真空电弧熔炼方法制备La-Mg-Ni/Co5：19和2：7型储氢合金.应用X射线衍射系统研究这两类合金的相结构,并测定各相的原子占位.研究表明：5：19型的（La1-xMgx）5Co19合金是由Pr5Co19,LaCo5和LaSb3V3种类型结构组成;在2：7型的（La1-xMgx）2Ni7合金中,除了（La0.85Mg0.15）2Ni7合金只含LaNi5类型相结构外,其他合金均含有LaNi5类型相结构及LaNi3或La2Ni7类型相之一.应用尝试法确定合金中各相的晶胞参数和体积的变化规律,并利用Rietveld全谱拟合分析方法测定了（La0.95Mg0.05）2Ni7合金的相结构及相含量.研究表明：两种储氢合金相结构中主相与晶界相的点阵常数之间存在良好的共格性.Mg原子同时部分取代La和Ni原子,随着Mg含量的增加,晶胞内空隙变大.由于吸收的H原子将占据这些空位,所以空位空间的增加有助于容纳更多的H.这暗示Mg原子的占位导致的晶体畸变与储氢合金储氢能力相关,同时由于Mg原子与H原子之间强的亲和力,以及主相与晶界相之间的共格关系,可以使得H原子更容易进人合金中,并形成稳定的相结构.     

氢在Zr(Cr,Fe)2第二相晶体中扩散的第一性原理研究

采用基于密度泛函理论的第一性原理方法,计算氢原子在Zr(Cr,Fe)_2(Fe/Cr=1∶7)晶体中的稳定间隙形成能。采用基于过渡态搜索理论的CI-NEB (climbing image nudged elastic band)方法预测氢原子在该晶体中的扩散路径及扩散势垒。研究结果表明,间隙氢原子在Zr(Cr,Fe)_2(Fe/Cr=1∶7)晶体中存在7种四面体间隙位(分别定义为ABCDEFG),7个间隙位均可稳定占据,其中G位点系统最稳定;最可能的扩散路径为B→C→D→E→F→G.     

Microstructure characterization and hydrogen storage properties study of Mg2Ni0.92M0.08 (M = Ti, V, Fe or Si) alloys

In the present study Mg_2Ni-type compounds alloyed independently with Ti,V,Fe and Si were successfully prepared by wet-milling followed by sintering.Although these alloyed Mg_2Ni compounds exhibited a similar hydrogen storage mechanism as that of pure Mg_2Ni,the dissolution of Ti,V or Fe into the Mg_2NiH_4lattice had a considerable catalytic effect on hydrogen desorption from additional MgH_2.The further structure investigations clearly indicated that the substitution of Ti for Ni could suppress the formation of the micro-twined low-temperature phase(LT2)and promote the formation of the high-temperature phase(HT),thus resulting in remarkably improved hydrogen desorption kinetics for the Mg_2Ni_(0.92)Ti_(0.08)–H system.     

Crystal structure and hydrogen storage properties of (La,Ce)Ni5-xMx (M=Al,Fe, or Co) alloys

The effects of partial substitution of La by Ce and Ni by Al, Fe, or Co in LaNi₅-based alloys on hydrogen storage performance were systematically studied. All samples were prepared using vacuum arc melting in an argon atmosphere. The results showed that for La-Ni_5-xM_x (M=Al, Fe, or Co) alloys, the lattice constants and unit cell volumes increased with an increasing amount of Al and Fe. On the other hand, these parameters decreased upon partial substitution of La by Ce. In addition, the lattice constant remained almost constant in the La_0.6Ce_0.4Ni_5-xCo_x alloys regardless of the value of x (x=0.3, 0.6, or 0.9), as Ce might enhance the homogeneity of the CaCu₅-type phase in Co-containing alloys. The hydrogen storage properties of the alloys were investigated using pressure, composition, and temperature isotherms. The experimental results showed that the plateau pressure decreased with an increasing content of Al, Fe, or Co, but it increased with Ce addition. Furthermore, the plateau pressures of all Co-containing alloys were almost identical upon substitution with Ce. Finally, the enthalpy (ΔH) and entropy (ΔS) values for all alloys were calculated using van't Hoff plots. The relationship between the lattice parameters and enthalpy changes for hydrogenation will be discussed.     

Hydrogen storage properties of (Ti0.85Zr0.15)1.05Mn1.2Cr0.6V0.1M0.1 (M=Ni, Fe, Cu) alloys easily activated at room temperature

The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)M_(0.1)(M=Ni, Fe, Cu) alloys with a single C14-type Laves phase have been fabricated by arc melting. They are able to be easily activated by one hydrogen absorption and desorption cycle under 4 MPa hydrogen pressure and vacuum at room temperature. Partial substitution of M for Mn results in the increase of hydrogenation and dehydrogenation capacities in an order of Ni Fe Cu. M elements increase the absorption and desorption plateau pressure in an order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1). The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1) alloy has reversible hydrogen capacities of 1.81 wt% at 273 K and 1.58 wt% at 318 K with formation enthalpy(ΔH_(ab)) of-20.66 kJ mol~(-1) and decomposition enthalpy(ΔH_(de)) of 27.37 kJ mol~(-1). The differences in the hydrogen storage properties can be attributed to the increase of the interstitial size for hydrogen accommodation caused by the increase of unit cell volumes in the order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1).     

LaNi_（5－x）Al_x贮氢合金的研究

用Ａｌ置换ＬａＮｉ５贮氢合金中部分Ｎｉ，得到一系列ＬａＮｉ（５－ｘ）Ａｌｘ（ｘ＝０．１，０．３，０．５）贮氢合金．通过对合金的热力学性能的测试可知：随着Ａｌ的加入及其含量的增加，贮氢合金的平台氢压降低，吸氢量有所减少，而吸氢速度有所增加．通过对合金及吸氢后氢化物品体结构的Ｘ射线衍射分析，发现Ａｌ的加入并未使晶体结构类型发生变化，只是晶格常数略有增加；同时还证明了ＬａＮｉ（５－ｘ）Ａｌｘ合金吸氢后其晶体结构也未发生变化，但晶格常数增加较大．     

稀土元素R对储氢合金(LaRMg)(NiCoAlZn)3.5相结构和电化学性能的影响

以(LaRMg)(NiCoAlZn)3.5(R=La、Ce、Pr、Nd、Gd、Y和Sc)合金为研究对象,研究稀土元素R部分替代La后对合金相结构和相组成及电化学性能的影响.XRD和EPMA方法分析结果表明,合金(LaRMg)(NiCoAlZn)3.5退火组织主要由Ce2Ni7型相(或Gd2Co7型)、PuNi3型相和CaCu5型相组成;Ce、Pr和Nd元素的替代对合金相组成没有明显影响,而Gd元素替代使合金中CaCu5型相明显减少,Ce2Ni7型(或Gd2Co7型)相显著增加,其相丰度达到79.03%;Y和Sc元素替代时合金中Gd2Co7型相基本消失.电化学测试和分析表明, 稀土元素R替代La后对合金电极活化性能影响不大,其中Nd、Gd、Y和Sc部分替代La在一定程度上提高合金的最大放电容量,而Gd元素替代时合金电极容量最高达到343.1 mAh/g;Gd和Nd元素部分替代La使合金电极的循环稳定性得到明显提高,S100分别达到95.3%和93.0%.此外,Sc部分替代La能有效改善合金电极的高倍率放电性能.     

MSn10(M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni)团簇的稳定性和磁性研究

采用密度泛函理论(density functional theory,DFT)中的广义梯度近似(generalized gradient approximation,GGA)对Sn11团簇的4种同分异构体(对称性分别为D5h,D5d,D4h,D4d)的几何结构、电子结构计算研究,得出对称性为D5d的团簇最稳定.将Sn11团簇的中心原子替换成过渡金属原子成为MSn10(M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni)团簇,对其稳定性和磁性进行了分析.在Sn11团簇中将中心原子替换成过渡金属原子后,束缚能都变小了,说明过渡金属原子的替换提高了原锡团簇的稳定性,其中NiSn10团簇的束缚能最小,稳定性最强.过渡金属原子都具有一定的磁性,当把这些原子掺入锡团簇后,过渡金属原子的磁性都有所减弱,其中MSn10(M=Sc,Ti,V,Ni)团簇的磁性完全消失,其原因在于掺杂后,团簇中各原子的电荷分布发生了变化.