Lithium (fluorosulfonyl)(n-nonafluorobutanesulfonyl)imide [Li[(FSO<sub>2sub>)(n-C<sub>4sub>F<sub>9sub>SO<sub>2sub>)N] (LiFNFSI)] is investigated as a conducting salt, which can form a relatively stable solid-electrolyte-interphase film in concentrated ether electrolyte to achieve favorable protection for lithium metal anodes. Li|Cu and Li|Li cells with concentrated LiFNFSI-based electrolyte have been demonstrated to display high average Coulombic efficiency (≈97%) and excellent cycling stability (over 1,000 h) of metallic lithium anodes, compared to concentrated lithium bis(trifluoromethanesulfonyl)imide [Li[N(SO<sub>2sub>CF<sub>3sub>)<sub>2sub>] (LiTFSI)]-based electrolyte. The morphologies and compositions of the lithium–metal anode surface are also comparatively analyzed by scanning electron microscopy and X-ray photoelectron spectroscopy, respectively. Moreover, superior electrochemical performance in the concentrated LiFNFSI-based electrolyte for Li|LiFePO<sub>4sub> cells is also presented herein. These results indicate that concentrated LiFNFSI-based electrolyte is a promising candidate for metallic lithium rechargeable batteries.
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