title: The Role of Cesium Cation in Controlling Interphasial Chemistry on Graphite Anode in Propylene Carbonate-Rich Electrolytes.
abstract: Despite the potential advantages it brings, such as wider liquid range and lower cost, propylene carbonate (PC) is seldom used in lithium-ion batteries because of its sustained cointercalation into the graphene structure and the eventual graphite exfoliation. Here, we report that cesium cation (Cs(+)) directs the formation of solid electrolyte interphase on graphite anode in PC-rich electrolytes through its preferential solvation by ethylene carbonate (EC) and the subsequent higher reduction potential of the complex cation. Effective suppression of PC-decomposition and graphite-exfoliation is achieved by adjusting the EC/PC ratio in electrolytes to allow a reductive decomposition of Cs(+)-(EC)m (1 ≤ m ≤ 2) complex preceding that of Li(+)-(PC)n (3 ≤ n ≤ 5). Such Cs(+)-directed interphase is stable, ultrathin, and compact, leading to significant improvement in battery performances. In a broader context, the accurate tailoring of interphasial chemistry by introducing a new solvation center represents a fundamental breakthrough in manipulating interfacial reactions that once were elusive to control.
authors.affiliation: School of Materials Science and Engineering, Hefei University of Technology , Hefei, Anhui 230009, People's Republic of China.
authors.forename: Hongfa
authors.initials: H
authors.lastname: Xiang
authors.forename: Donghai
authors.initials: D
authors.lastname: Mei
authors.forename: Pengfei
authors.initials: P
authors.lastname: Yan
authors.forename: Priyanka
authors.initials: P
authors.lastname: Bhattacharya
authors.forename: Sarah D
authors.initials: SD
authors.lastname: Burton
authors.affiliation: Sensor and Electron Devices Directorate, U.S. Army Research Laboratory , Adelphi, Maryland 20783, United States.
authors.forename: Arthur
authors.initials: A
authors.lastname: von Wald Cresce
authors.forename: Ruiguo
authors.initials: R
authors.lastname: Cao
authors.forename: Mark H
authors.initials: MH
authors.lastname: Engelhard
authors.forename: Mark E
authors.initials: ME
authors.lastname: Bowden
authors.forename: Zihua
authors.initials: Z
authors.lastname: Zhu
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Bryant J
authors.initials: BJ
authors.lastname: Polzin
authors.forename: Chong-Min
authors.initials: CM
authors.lastname: Wang
authors.affiliation: Sensor and Electron Devices Directorate, U.S. Army Research Laboratory , Adelphi, Maryland 20783, United States.
authors.forename: Kang
authors.initials: K
authors.lastname: Xu
authors.forename: Ji-Guang
authors.initials: JG
authors.lastname: Zhang
authors.forename: Wu
authors.initials: W
authors.lastname: Xu
keywords: cesium cation; electrolyte; graphite exfoliation; propylene carbonate; solid electrolyte interphase