Characteristics of tetrahydrofuran-based electrolytes with magnesium alkoxide additives for rechargeable magnesium batteries

The electrochemical behavior of magnesium (Mg) metal was investigated in tetrahydrofuran (THF)-based solutions containing magnesium bromide (MgBr2) and/or magnesium ethoxide (Mg(OEt)(2)). THF solutions containing a single solute, MgBr2 or Mg(OEt)(2), show no visible faradaic current based on Mg deposition and/or dissolution. However, the electrolyte system containing both solutes, MgBr2 + Mg(OEt)(2)/THF, gives a reversible current response of Mg deposition and dissolution. The ionic structure of the electrolyte system containing the binary solute was examined by infrared (IR) spectroscopy and density functional theory (DFT) calculations, It was confirmed that MgBr2 and Mg(OEt)(2) are coordinated (solvated) with THF molecules to form an EtO-Mg-Br-4THF complex. The DFT calculations also suggest the possible formation of-complexes for the MgBr2/Mg(OEt)(2) binary system in THF. The voltammetric responses at the Pt electrode indicate low overpotential and high coulombic efficiency for Mg deposition and dissolution in THF-based solutions containing suitable molar ratios of MgBr2 and Mg(OEt)(2). The constant-current charge-discharge cycling of Mg in MgBr2 + Mg(OEt)(2)/THF electrolyte also shows low overpotential and good cyclability over 300 cycles. (C) 2016 Elsevier B.V. All rights reserved.