Si_n团簇/石墨烯(n≤6)结构稳定性和储锂性能的第一性原理计算

目前,硅/碳复合材料是锂离子电池最有潜在应用前景的高容量负极材料之一,硅与碳材料的界面状态是影响其电化学性能的重要因素.本文在作为碳材料结构单元的石墨烯表面构建了 Si_n(n≤6)团簇,采用基于密度泛函理论(DFT)的第一性原理方法研究了 Si_n团簇/石墨烯(Si_n/Gr)的几何构型、结构稳定性和电子性质.结果表明,当Si原子数n≤4时,Si_n团簇优先以平行于石墨烯的二维构型沉积在石墨烯表面,当n ≥ 5时,Si_n团簇优先以三维立体构型沉积在石墨烯表面.随着n的增大,Si_n团簇在石墨烯表面的热力学稳定性显著降低,两者之间的界面结合减弱,并且伴随着Si_n团簇与石墨烯之间的电荷转移也越来越少.同时还研究了Si_n/Gr复合构型的储锂能力,Li原子主要存储在Si_n团簇临近的石墨烯表面和Si_n团簇周围,Si_n团簇与石墨烯复合形成的协同作用增强了 Li原子吸附的热力学稳定性.当n≤4时,存储2个Li原子有利于提高xLiSi_n/Gr体系的热力学稳定性,继续增加Li原子数x会导致稳定性降低;当n≥5时,稳定性随着Li原子数x的增多而逐渐降低.     

石墨烯吸附Li团簇的第一性原理计算

构建了单层六方石墨烯超晶胞结构,以吸附不同尺寸的Li团簇,Li:C摩尔比例皆为1:6.采用基于密度泛函理论的第一性原理,计算了其态密度、差分电荷密度、能带,分析了Li团簇与石墨烯吸附前后的电荷分布情况及Li-C成键类型,二者之间的电荷分布决定了两者的相互作用.使用热力学的方法及成核机制进行分析,得出成核的可能性与团簇尺寸的关系,研究了一定浓度下的锂在石墨烯上的成核问题.相应的计算结果有助于理论上深入理解锂电池储能机理.     

石墨烯形核初期Cu(111)面上C_xH_y团簇生成的理论研究

采用基于密度泛函理论的第一原理计算方法,我们研究了Cu(111)表面上石墨烯成核生长过程中CxHy小团簇的吸附和生成行为.计算结果表明:随着氢原子饱和度、氢原子个数的增大,CxHy团簇的形成能减小,碳原子与铜表面的平均距离增加,C-C键的平均键长呈增大趋势.然而,当生成的CxHy团簇具有空间对称结构时,在一定程度上打破了上述规律性.令人惊奇的是,形成的C3H4和C3H5对称团簇具有类似石墨烯的空间结构,这类结构可能在石墨烯的形成过程中起着重要的作用.     

石墨烯形核初期Cu(111)面上CxHy团簇生成的理论研究

采用基于密度泛函理论的第一原理计算方法,我们研究了Cu(111)表面上石墨烯成核生长过程中CxHy小团簇的吸附和生成行为. 计算结果表明：随着氢原子饱和度、氢原子个数的增大,CxHy团簇的形成能减小,碳原子与铜表面的平均距离增加,C-C键的平均键长呈增大趋势. 然而,当生成的CxHy团簇具有空间对称结构时,在一定程度上打破了上述规律性. 令人惊奇的是,形成的C3H4和C3H5对称团簇具有类似石墨烯的空间结构,这类结构可能在石墨烯的形成过程中起着重要的作用.     

锂离子电池硅基负极材料嵌锂行为的第一性原理研究

采用基于密度泛函理论的第一性原理平面波赝势方法,计算不同数量的锂离子引起的硅材料晶体结构的变化以及在嵌锂过程中形成Li_xSi(x=1、2、2.4、4.4)合金相的形成能与电子结构.采用LST/QST方法计算过渡态,模拟合金体相中的锂离子迁移过程.计算结果表明,随着嵌锂数量的增加,硅晶胞的体积在不断增大;Li_xSi合金相的形成能为负值,表明在嵌锂过程中锂离子和硅原子可以自发形成这些合金相,其中Li₇Si₃合金最容易形成;随着嵌锂量的增加,锂离子在费米能级处s轨道提供的电子数逐渐增加,锂硅合金在费米能级处的电子数量呈增大趋势,表明锂硅合金的导电性越来越优;常温下Li₂Si体相中很难直接形成锂离子空位,但锂离子空位的迁移过程很容易发生.     

GaSi_n(n=1-6)团簇结构和稳定性的第一性原理研究

采用密度泛函理论(DFT),在B3LYP/6-311+G(d)水平下研究了GaSi_n(n=1-6)团簇的几何构型、电子性质、稳定性和振动特性.研究结果表明:GaSi_n(n=1-6)团簇基态结构基本保持了纯硅团簇的结构框架,Ga原子往往被吸附在Sin团簇的表面上.布局分析显示电子由Ga原子向Sin框架转移.平均束缚能和分裂能表明GaSi_3和GaSi_5团簇相对其他团簇具有较强的稳定性.振动特性研究表明:GaSi_n(n=1-6)团簇的IR活性最强振动模式主要是Ga原子与Sin结构之间的相对振动.极化率的研究表明,随着Si原子数的增多,GaSi_n团簇的非线形光学效应逐渐增强,更容易被外场极化.     

锂改性点缺陷石墨烯储氢性能的第一性原理研究

本研究采用基于密度泛函理论的第一性原理方法计算了两种石墨烯点缺陷处原子的分波态密度(PDOS),能带结构和差分电荷密度等,研究了锂掺杂对两种本征石墨烯缺陷C-Bridge和C7557电子结构的改性,以及对其储氢能力的影响.结果表明Li原子能够稳定的掺杂且不易形成团簇,并且Li原子掺杂石墨烯能够对石墨烯能带中的狄拉克锥和费米面起到调控作用,增强了缺陷石墨烯的电子活性.本征缺陷石墨烯的储氢能力较弱,缺陷石墨烯的储氢能力可以通过Li掺杂来改善.     

NO在Ni_xAg_y(x+y=13)团簇表面吸附分解的第一性原理研究

基于第一性原理计算方法,对Ni_xAg_y(x+y=13)团簇的几何结构进行优化后,研究了NO在此类团簇表面不同位置的吸附分解行为,讨论了团簇的束缚能、束缚能的二阶差分、能隙以及吸附前后键长、吸附能、NO分波态密度的变化情况.结果表明,团簇对称性随着Ni的占比变化而变化,稳定性随Ni占比增加而增强,束缚能的二阶差分随着Ni原子的增多呈现奇偶震荡性,NO@Ni_xAg_y(x+y=13)团簇表面吸附行为主要为化学吸附,吸附后N-O键长的变化在0.028?～0.092?之间.对团簇吸附NO的态密度分析发现,吸附后NO的2π*轨道失去电子,1π轨道得到电子,从而导致吸附能的变化.     

低温下Au959团簇负载于MgO(100)表面后结构变化的分子动力学研究

采用基于Chen-Mbius反演方法,从金属/金属氧化物界面第一性原理计算的粘结能结果中推导出的Au/MgO原子间相互作用势的正则系综(NVT)分子动力学,模拟了在10 K条件下,Au959团簇负载于MgO(100)表面后团簇结构的变化.根据原子对分析技术和对分布函数的分析表明,由于团簇界面处原子间距与载体原子间距相匹配,置于载体上的Au团簇经过一个变形过程后,较其孤立自由表面时的团簇体积变大.     

HmTiSin(m=1～2;n=2～8)团簇结构、电子性质和红外光谱的密度泛函理论研究

近些年,由于硅半导体材料在微电子工业中的潜在应用,其理论和实验研究备受人们广泛关注。尤其是过渡金属掺杂的硅团簇材料在物理化学性质方面表现了极好的稳定性。这些主要归因于过渡金属含有未填满的d轨道电子,可以填充硅团簇表面的空轨道,减少团簇表面的悬挂键,进而提高整个掺杂硅团簇的结构稳定性,同时产生各种特殊光学、磁性和超导等性质。采用密度泛函理论DFT-B3LYP方法对H_mTiSi_n(m=1～2; n=2～8)团簇的几何结构和电子性质进行了理论计算,讨论了Ti掺杂硅团簇TiSi_n(n=2～8)及其氢化团簇基态结构的变化规律、解离通道和HOMO-LUMO能隙等特征。结果表明,随着Si原子数目的增加,在TiSi_n(n=2～8)团簇中其掺杂Ti原子依次吸附在团簇的棱、面及结构内部。当在掺杂团簇表面吸附氢原子时,都优于吸附在团簇的硅原子上,而且绝大多数的氢化结构采纳了TiSi_n团簇的骨架构型。解离能和HOMO-LUMO能隙的分析结果表明在团簇表面吸附两个H原子时能够明显提高整个团簇的结构稳定性。二阶能量差分的研究发现TiSi₂和TiSi₆团簇相对其他团簇具有较高的稳定性,同时两个H₁TiSi₇和H₂TiSi₇氢化团簇的稳定性更高。此外,模拟了这些氢化团簇的红外振动特征峰,对主要特征峰进行了归属。这些研究将为过渡金属掺杂硅基团簇材料的实验制备和表征提供重要的理论参考。     

Structures of Pt clusters on graphene doped with nitrogen, boron, and silicon: a theoretical study

The structures of Pt clusters on nitrogen-,boron-,silicon-doped graphenes are theoretically studied using densityfunctional theory.These dopants(nitrogen,boron and silicon) each do not induce a local curvature in the graphene and the doped graphenes all retain their planar form.The formation energy of the silicon-graphene system is lower than those of the nitrogen-,boron-doped graphenes,indicating that the silicon atom is easier to incorporate into the graphene.All the substitutional impurities enhance the interaction between the Pt atom and the graphene.The adsorption energy of a Pt adsorbed on the silicon-doped graphene is much higher than those on the nitrogen-and boron-doped graphenes.The doped silicon atom can provide more charges to enhance the Pt-graphene interaction and the formation of Pt clusters each with a large size.The stable structures of Pt clusters on the doped-graphenes are dimeric,triangle and tetrahedron with the increase of the Pt coverage.Of all the studied structures,the tetrahedron is the most stable cluster which has the least influence on the planar surface of doped-graphene.     

Photothermal investigation study of porous silicon layer doped lithium

This paper presents a series of experimental photothermal deflection technique (PTD) spectra of porous silicon layers doped with lithium on crystalline silicon backing (PS/Li) and their numerical analysis. The aim of this work is to investigate the influence of Li doping on the opto-thermal properties (optical absorption, band-gap energy, thermal diffusivity and thermal conductivity). Also, we correlate these results with other evaluation studies such as I–V measurements and atomic force microscope analysis performed on the material. We observe a red shift of the gap, which can be related to the reduction of crystallite size. Moreover, we notice a decrease of thermal properties with the same behavior as electrical conductivity.     

锂原子修饰硼原子链团簇的结构和储氢性能研究

采用密度泛函方法对锂原子修饰线型硼原子链团簇Li_2B_n(n=2~8)的结构及其储氢性能进行理论研究.结果显示,Li原子可键合于硼链团簇的两端,氢能以分子形式吸附在Li原子周围,每一个Li原子最多可吸附4个氢分子,氢分子的平均吸附能为2.020~2.832 kcal.mol~(-1).其中Li原子修饰B2小团簇的质量储氢分数最大,为31.24 wt%,表明在常温常压条件下它有可能成为一种潜在的储氢媒介.     

锂原子修饰硼原子链团簇的结构和储氢性能研究

采用密度泛函方法对锂原子修饰线型硼原子链团簇Li2Bn(n=2~8)的结构及其储氢性能进行理论研究. 结果显示, Li原子可键合于硼链团簇的两端,氢能以分子形式吸附在Li原子周围, 每一个Li原子最多可吸附4个氢分子, 氢分子的平均吸附能为2.020 ~ 2.832 kcal.mol-1. 其中Li原子修饰B2小团簇的质量储氢分数最大,为31.24 wt%,表明在常温常压条件下它有可能成为一种潜在的储氢媒介.     

Effects of nitrogen on the carbon anode of a lithium secondary battery

Nitrogen-containing carbons have been made from different polymer precursors at 600°C. Their composition and structure have been studied by chemical analysis, X-ray powder diffraction and X-ray photoelectron spectroscopy. These results show that this kind of carbon is disordered, and nitrogen exists as two kinds of forms in the polymeric carbons: graphene nitrogen (N_1s binding energy 398.5 eV) and conjugated nitrogen (N_1s binding energy 400.2 eV). The discharge and charge process suggests that these two kinds of nitrogen are bonded satisfactorily and could not result in irreversible reaction with Li. The increase of reversible capacity mainly results from the graphene nitrogen, and the higher the content of nitrogen, the higher the charge capacity. Part of the irreversible capacity is derived from the formed lithium carbide and lithium atoms which are intercalated and could not be deintercalated.     

CLi+5超碱团簇的结构及储氢性能的理论研究

利用密度泛函理论( B3LYP) 方法，在 6 - 311 + + G ( d,p) 基组水平上，对超碱团簇 CLi₅及其阳离子体系 CLi₅⁺的几何结构和稳定性等物理化学性质进行理论计算，并进一步研究它们的储氢性能． 分析可知，CLi₅⁺超碱离子团簇结构相比中性 CLi₅团簇结构动力学稳定性要高，表面吸氢能力更强． 氢分子在 CLi₅⁺表面能以介于物理吸附与化学吸附之间的形式吸附，每个 Li 原子最多可以有效吸附三个 H₂，平均吸附能处于 1. 065 ～ 2. 732 k Cal/mol 范围内，储氢质量分数可达 39. 30 wt % ，表明 CLi₅⁺超碱离子团簇可以作为一种理想的储氢材料．     

Equilibrium geometries and electronic properties of BenLi （n=2-15） clusters from first principles

This paper studies the equilibrium geometries and electronic properties of Ben and BenLi clusters, up to n=15, by using density-functional theory（DFT） at B3LYP/6-31G（d） level. The lowest-energy structures of Ben and BenLi clusters were determined. The results indicate that a single lithium impurity enhances the stability and chemical reactivity of the beryllium clusters. It finds that the geometries of the host clusters change significantly after the addition of the lithium atom for n ≥8. The lithium impurity prefers to be on the periphery of beryllium clusters, and occupies vertex sites. Both Be4Li, Be9Li, and Be13Li were found to be particularly stable with higher average binding energy, local peaks of second-order energy difference and fragmentation energies. For all the BenLi clusters studied, we found charge transfers from the Li to Be site and co-existence of covalent and metallic bonding characteristics.     

Characterization of a hybrid Li-ion anode system from pulsed laser deposited silicon on CVD-grown multilayer graphene

A hybrid anode system for lithium (Li) ion battery applications based on pulsed laser deposited silicon films on chemical vapor deposited multilayer graphene (MLG) layers on a nickel foam substrate was electrochemically characterized. The as-grown material was directly fabricated into an anode without a binder, and tested in a half-cell configuration. There is evidence of the participation of both the multilayer graphene and the Si in the transport of Li ions. Even when cycled under stressful voltage limits that accelerate degradation, the MLG–Si films displayed higher stability than Si-only anodes, especially at higher cycling rates. Unlike the Si cells that display capacity fade even within the first few cycles, the MLG–Si cells show a very narrow spread in capacity, indicative of the role of the graphene layers in improving adhesion of the Si and acting as a compliant buffer for its volume expansion. Stable average specific capacities of ~1,200 mAh/g per total weight of MLG + Si, over 80 cycles at C/5 rate, were obtained for the MLG–Si anode. Pre- and post-cycling characterization of the anode materials revealed the differences between the two systems.     

The Ground State Energy of the Hypernucleus Λ6Li

This paper extends the method of the harmonic-oscillator product state as basis function to the hypernucleus A6Li which is of non-zero spin. we have studied the characteristic of the ground state of the hypernucleus A6Li with this method and an α+ p + A three cluster model. The calculated result shows the method can be used to calculate the energy level of the system in which the interaction between the constituent clusters is spin-dependent.