Synergetic Role of Li + during Mg Electrodeposition/Dissolution in Borohydride Diglyme Electrolyte Solution: Voltammetric Stripping Behaviors on a Pt Microelectrode Indicative of Mg–Li Alloying and Facilitated Dissolution

Abstract

We describe a voltammetric and spectroscopic study of Mg electrodeposition/dissolution (Mg-Dep/Dis) in borohydride diglyme electrolyte solution containing Li+ carried out on a Pt ultramicroelectrode (UME, r = 5 mu m). The data reveal Li+ cation facilitation that has not been previously recognized in studies made using macroelectrodes. While a single broad, asymmetric stripping peak is expected following MgDep on a Pt macroelectrode in 0.1 M Mg(BH4)(2) + 1.5 M LiBH4 diglyme solution on a Pt UME, the stripping reveals three resolved oxidation peaks, suggesting that Mg-Dep/Dis consists of not only a Mg/Mg2+ redox reaction but also contributions from MgLi alloying/dissolution reaction processes. Detailed XPS, SIMS, ICP, and XRD studies were performed that confirm the importance of MgLi alloy formation processes, the nature of which is dependent on the reduction potential used during the MgDep step. Based on the electrochemical and surface analysis data, we propose an electrochemical mechanism for Mg-Dep/Dis in a borohydride diglyme electrolyte solution that, in the presence of 1.5 M Li+ ions, proceeds as follows: (1) Mg2+ + 2e (sic) Mg; (2) (1 x)Mg2+ + xLi+ + (2 x)e (sic) Mg(1x)Lix, 0 < x (sic) 0.02; and (3) (1 y)Mg2+ + yLi+ + (2 y)e (sic) Mg(1y)Liy, 0.02 < y <= 0.09. Most significantly, we find that the potential-dependent Mg-Dep/Dis kinetics are enhanced as the concentration of the LiBH4 in the diglyme electrolyte is increased, a result reflecting the facilitating influences of reduced uncompensated resistance and the enhanced electro-reduction kinetics of Mg2+ due to Mg-Li alloy formation.