第一性原理计算应用于锂硫电池研究的评述  

Review on the First-Principles Calculation in Lithium-Sulfur Battery

作　　者：张晓菲 李燊昊 汪震 闫健 刘家琴 吴玉程 Xiaofei Zhang;Shenhao Li;Zhen Wang;Jian Yan;Jiaqin Liu;Yucheng Wu(Institute of Industry&Equipment Technology,School of Materials Science and Engineering,Key Laboratory of Advanced Functional Materials&Devices of Anhui Province,Hefei University of Technology,Hefei 230009,China)

机构地区：[1]合肥工业大学工业与装备技术研究院,材料科学与工程学院先进功能材料与器件安徽省重点实验室,合肥230009

出　　处：《化学进展》2023年第3期375-389,共15页Progress in Chemistry

基　　金：国家自然科学基金项目(No.51972093,U1810204,U1910210);安徽省自然科学基金项目(No.2008085ME129);安徽省重点研究与开发计划(No.202004b11020024);中央高校基本科研业务费专项资金(No.PA2021GDSK0087)资助。

摘　　要：锂硫电池凭借超高理论容量和能量密度以及硫储量丰富和环境友好等优势被认为是极具发展前景的新一代高能电池体系。然而,活性硫及放电终产物导电性差、多硫化物穿梭效应、硫反应动力学缓慢等关键问题严重制约了其实际应用。研究人员采用硫正极设计、功能隔膜/中间层、电解质改性或固体电解质等策略,在解决以上问题方面取得重要进展。然而,针对锂硫电池内部实时动态反应过程、规律和机制以及电极/电解质界面设计调控策略仍缺乏深入认识。第一性原理计算逐渐发展为化学、材料、能源等诸多学科领域的重要研究工具,有助于从原子/分子水平理解反应中间产物性质、分子/电子间相互作用、电化学反应过程和规律、电极/电解质动态演化过程等,相较于“实验试错法”,其在研究锂硫电池内部多电子和多离子氧化还原反应方面具有显著优势。本文全面综述了运用第一性原理计算研究锂硫电池电极与多硫化物相互作用、充放电反应机制以及电解质三个方面的重要进展,展望了第一性原理计算应用于锂硫电池研究的当前挑战和未来发展方向。Lithium-sulfur(Li-S)batteries are considered as a promising next-generation high-energy battery system due to their ultrahigh theoretical capacity,energy density and the merits of sulfur in terms of abundant resource and environmental friendliness.However,their practical application is confronted with several critical problems including insulation of sulfur and discharge products,shuttle effect of soluble lithium polysulfides,and sluggish reaction kinetics of sulfur,etc.Significant progress has been achieved in addressing these problems by sulfur electrode design,functional separator/interlayer,liquid-electrolyte modification,and solid-electrolyte strategy.Nevertheless,there is still a lack of in-depth understanding of real-time dynamic reaction process and mechanism as well as electrode/electrolyte interface regulation strategy in Li-S batteries.First-principles calculation has gradually developed into an important research tool in various disciplines such as materials,chemistry and energy,facilitating to understand the properties of reaction species,interactions between molecules or/and electrons,electrochemical reaction processes and laws,and dynamic evolution of electrode/electrolyte from the molecular/atomic level.It delivers distinct advantages beyond“experimental trial and error”method in studying the multi-electron and multi-ion redox process in Li-S battery.In this paper,important advances in the application of first principles calculation to study the interactions between electrodes and polysulfides,charge-discharge reaction mechanisms,and electrolytes in Li-S batteries are comprehensively reviewed,and the current challenge and enlightening directions for application of first-principles calculation to study Li-S batteries are also prospected.

关 键 词：锂硫电池 第一性原理 理论计算 电极材料 充放电机理 电解质 

分 类 号：O643[理学—物理化学] O646[理学—化学] TM911[电气工程—电力电子与电力传动]