Abstract
The lithium(Li)metal batteries(LMBs)are considered one of the most promising next-generation batter-ies due to its extremely high theoretical specific capacity.However,there are a couple of issues,e.g.,the serious side reactions that occurred at the solid-liquid interface between the electrolyte and Li metal an-ode,hindering the broad commercialization of LMBs.Thus,a comprehensive understanding of the mech-anisms underlying the decomposition of electrolytes is crucial to the design of LMBs.Herein,we utilize density functional theory simulations to explore the decomposition mechanism of electrolytes.The most commonly used ether electrolyte solvents,i.e.,1,2-dimethoxyethane(DME)and 1,3-dioxalane(DOL),based on suitable lithium salts,namely bis(trifluoromethanesulfonyl)imide(LiTFSI),are chosen to model the ac-tual situations.We explicitly demonstrate that an electron-rich environment near the interface accelerates the decomposition of electrolytes.For ether electrolytes,we show that the LiTFSI degradation path is de-pending on the ratio of DOL to DME.In addition,the solvation structures of lithium-ion undergo a series of transformations upon electrolyte degradation,becoming thermodynamically more favorable and having a higher reduction potential in an electron-rich environment.Our finding provides new insights into the decomposition mechanisms of electrolytes and paves the way for the rational design of high-performance LMBs.
基金项目
国家重点研发计划(2022YFE0113800)
国家自然科学基金(U21A20174)
国家自然科学基金(52225208)
国家自然科学基金(51972285)
浙江省自然科学基金(LY23E020010)
funding of"Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang"(2020R01002)
NETL
NSTL
万方数据