Investigation of Fluorinated Amides for Solid–Electrolyte Interphase Stabilization in Li–O2 Batteries Using Amide-Based Electrolytes

Solvent and electrode stability is critical for the successful development of the rechargeable, organic electrolyte Li–O2 (air) battery. Straight-chain alkyl amides, such as N,N-dimethylacetamide (DMA), show superior stability at the O2 cathode compared to organic carbonates and glymes, but these solvents do not form a stable solid–electrolyte interphase (SEI) to prevent a sustained reaction with Li metal. In this work, we use electrochemical impedance spectroscopy and cycling tests on a symmetric Li/electrolyte/Li cell to determine the ability of several fluorinated amide solvents to stabilize the lithium/electrolyte interface. The LiTFSI/N,N-dimethyltrifluoroacetamide (DMTFA) system shows the smallest interfacial impedance and the lowest polarization for Li dissolution and deposition. We present quantum chemical calculations indicating that α-fluorinated alkyl amides are reduced on Li to form insoluble LiF with no or little activation energy. XPS analysis confirms the presence of LiF in the SEI on Li me...

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