LAUSR

Li metal provides an ideal anode for the highest energy density batteries, but its reactivity with electrolytes brings poor cycling stability. Electrolyte additives have been employed to effectively improve the cycling stability, often with the underlying mechanism poorly understood. In this work, applying lithium bis(oxalate)borate (LiBOB) as a chemical source for a dense and protective interphase, we investigate this issue with combined techniques of electrochemical/physical characterizations and theoretical calculations. It was revealed that the solid electrolyte interphase (SEI) formed by Li and the carbonate electrolyte is unstable and responsible for the fast deterioration of the Li anode. When LiBOB is present in the electrolyte, a reinforced SEI was formed, enabling significant improvement in cycling stability due to the preferential reduction of the BOB anion over the carbonate molecules and the strong combination of its reduction products with the species from the electrolyte reduction. The effectiveness of such new SEI chemistry on the Li anode supports excellent performance of a Li/LiFePO4 cell. This approach provides a pathway to rationally design an interphase on the Li anode so that high energy density batteries could be realized.