title: Role of Chloride for a Simple, Non-Grignard Mg Electrolyte in Ether-Based Solvents.
abstract: Mg battery operates with Chevrel phase (Mo6S8, ∼1.1 V vs Mg) cathodes that apply Grignard-based or derived electrolytes, which allow etching of the passivating oxide coating forms at the magnesium metal anode. Majority of Mg electrolytes studied to date are focused on developing new synthetic strategies to achieve a better reversible Mg deposition. While most of these electrolytes contain chloride as a component, and there is a lack of literature which investigates the fundamental role of chloride in Mg electrolytes. Further, ease of preparation and potential safety benefits have made simple design of magnesium electrolytes an attractive alternative to traditional air sensitive Grignard reagents-based electrolytes. Work presented here describes simple, non-Grignard magnesium electrolytes composed of magnesium bis(trifluoromethane sulfonyl)imide mixed with magnesium chloride (Mg(TFSI)2-MgCl2) in tetrahydrofuran (THF) and diglyme (G2) that can reversibly plate and strip magnesium. Based on this discovery, the effect of chloride in the electrolyte complex was investigated. Electrochemical properties at different initial mixing ratios of Mg(TFSI)2 and MgCl2 showed an increase of both current density and columbic efficiency for reversible Mg deposition as the fraction content of MgCl2 increased. A decrease in overpotential was observed for rechargeable Mg batteries with electrolytes with increasing MgCl2 concentration, evidenced by the coin cell performance. In this work, the fundamental understanding of the operation mechanisms of rechargeable Mg batteries with the role of chloride content from electrolyte could potentially bring rational design of simple Mg electrolytes for practical Mg battery.
authors.forename: Niya
authors.initials: N
authors.lastname: Sa
authors.forename: Baofei
authors.initials: B
authors.lastname: Pan
authors.affiliation: Department of Chemistry, Indiana University , Bloomington, Indiana 47405, United States.
authors.forename: Anumita
authors.initials: A
authors.lastname: Saha-Shah
authors.forename: Aude A
authors.initials: AA
authors.lastname: Hubaud
authors.forename: John T
authors.initials: JT
authors.lastname: Vaughey
authors.affiliation: Department of Chemistry, Indiana University , Bloomington, Indiana 47405, United States.
authors.forename: Lane A
authors.initials: LA
authors.lastname: Baker
authors.forename: Chen
authors.initials: C
authors.lastname: Liao
authors.forename: Anthony K
authors.initials: AK
authors.lastname: Burrell
keywords: Chevrel phase cathode; Mg battery; nonaqueous Mg electrolyte; plating and stripping of magnesium; rechargeable magnesium battery