InSb的Li嵌入电压轮廓曲线从头计算

InSb是很有应用前途的Li离子电池非碳类负极材料. 使用基于密 度泛函理论的第一原理赝势法，计算了InSb 在Li嵌入时的125种不同情况下的总能、形成能 以及平衡体积等，进而参考电压轮廓实验曲线，筛选出了若干条理论上可能的反应路径，得到了Li嵌入时的电压轮廓曲线. 结果表明，从体InSb相到Li＿3Sb相之间没有中间经历五个相及五个相以上的反应路径；中间经历一个相的最可能反应过程为Li+In＿4Sb＿4→Li＿1In＿4Sb＿4,11Li+Li＿1In＿4Sb＿4→Li＿12Sb＿4+4In；中间经 历四个相的仅有一条反应路径：Li+In＿4Sb＿4→Li＿1In＿4Sb＿4,2Li+Li＿1In＿4Sb＿4→ Li＿3In＿4Sb＿4,4Li+Li＿3In＿4Sb＿4→Li＿7In＿3Sb＿4+In,3Li+Li＿7In＿3Sb＿4→Li＿10In＿2Sb＿4+In,2Li+Li＿10In＿2Sb＿4→Li＿12Sb＿4+2In.关键词：InSbLi嵌入电压轮廓曲线从头计算

Ab initio calculation of the voltage profile curve of Li insertions in lnSb

InSb is an important non-carbon-bearing anode material for lithium (ion) batteri es. An ab initiomethod with first-principles pseudopotentials based on the density functional theory has been used to calculate the total energies, formation energies and equi librium volumes of Li intercalations in InSb in 125 possible cases. Comp aring with the experimental voltage profile curve, we have picked out the possib le reaction routes of Li insertions in InSb and a theoretical voltage pr ofile curve is reached. Our results show that, from bulk InSb to bulk Li＿3Sb, the re are no possible reaction routes undergoing five or more intermediate ph ases. The most favored route for undergoing only one intermediate phase is Li+In＿4Sb＿4→Li＿1In＿4Sb＿4,11Li+Li＿1In＿4Sb＿4→Li＿12Sb＿4+4In；whereas there exists only one reaction route for undergoing four intermediate phases, that is, Li+In＿4Sb＿4→Li＿1In＿4Sb＿4,2Li+Li＿1In＿4Sb＿4→ Li＿3In＿4Sb＿4,4Li+Li＿3In＿4Sb＿4→Li＿7In＿3Sb＿4+In,3Li+Li＿7In＿3Sb＿4→Li＿10In＿2Sb＿4+In,2Li+Li＿10In＿2Sb＿4→Li＿12Sb＿4+2In..