Adiponitrile (ADN), which generally exhibits high anodic stability, is a troublesome solvent in a lithium electrolyte due to an inability to form a robust and stable solid electrolyte interface (SEI) on an anode, which hinders its application as single solvent in lithium ion batteries (LIBs). In this work, we describe addition of small quantities of nitronium tetrafluoroborate (NO2BF4) to an ADN based Li electrolyte that resulted in three major benefits. Firstly, NO2BF4 distinctively modified the otherwise unstable SEI, by forming a robust thin Li2O/LiF laden SEI capable of mitigating relevant detrimental surface side reactions at the electrode, therefore enabling remarkably stable and reversible electrochemical plating/stripping of Li on metallic substrates and/or Li, without the need for a co-solvent. Secondly, in contrast to typical indications of dendritic nucleation in carbonate electrolytes, effective suppression of dendritic growth and stable cycling was evidenced in an no2bf4 containing ADN electrolyte. Thirdly, the above achievements were realized with no negative effect of the additive on the anodic stability of the electrolyte, which provided impetus to test high voltage operation at 20 C. Lithium battery incorporating Li anode/LiMn2O4 assembled using the additive containing electrolyte displayed good reversible capacity and cyclic retention (100 mAhg-1 at 1C for 200 cycles) and when tested at potentials >5.6 V at high C rates (12C), showed stable capacity (90.7 mAhg-1), and remarkable cooperation of Li anode and anodic suppression in anodic electrolyte decomposition.