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The electrolytes for lithium metal batteries (LMBs) are plagued by a low Li+ transference number (T+) of conventional lithium salts and inability to form a stable solid electrolyte interphase (SEI). Here, we synthesized a self‐folded lithium salt, lithium 2‐[2‐(2‐methoxy ethoxy)ethoxy]ethanesulfonyl(trifluoromethanesulfonyl) imide (LiETFSI), and comparatively studied with its structure analogue, lithium 1,1,1‐trifluoro‐N‐[2‐[2‐(2‐methoxyethoxy)ethoxy)]ethyl]methanesulfonamide (LiFEA). The special anion chemistry imparts the following new characteristics: i) In both LiFEA and LiETFSI, the ethylene oxide moiety efficiently captures Li+, resulting in a self‐folded structure and high T+ around 0.8. ii) For LiFEA, a Li−N bond (2.069 Å) is revealed by single crystal X‐ray diffraction, indicating that the FEA anion possesses a high donor number (DN) and thus an intensive interphase "self‐cleaning" function for an ultra‐thin and compact SEI. iii) Starting from LiFEA, an electron‐withdrawing sulfone group is introduced near the N atom. The distance of Li−N is tuned from 2.069 Å in LiFEA to 4.367 Å in LiETFSI. This alteration enhances ionic separation, achieves a more balanced DN, and tunes the self‐cleaning intensity for a reinforced SEI. Consequently, the fast charging/discharging capability of LMBs is progressively improved. This rationally tuned anion chemistry reshapes the interactions among Li+, anions, and solvents, presenting new prospects for advanced LMBs. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel lithium salt lithium bis(4-styrene) sulfonyl imine (LiBSSI) is synthesized. • Li+ deposition in cells with P(PETMP-LiBSSI)/PVDF-HFP SICPEs is regulated uniformly to avoid lithium dendrite growth. • P(PETMP-LiBSSI)/PVDF-HFP SICPEs show high t Li+ (0.95) and a wide electrochemical stability window (5.85 V vs. Li/Li+). • Li|P(PETMP-LiBSSI)/PVDF-HFP|Li battery exhibits superior cycle stability at ambient temperature. In spite of the fact that lithium metal batteries (LMBs) facilitate the diversification of energy storage technologies, their electrochemical reversibility and stability have long been constrained by side reactions and lithium dendrite problems. While single-ion conducting polymer electrolytes (SICPEs) possess unique advantages of suppressing Li dendrite growth, they deal with difficulties in practical applications due to their slow ion transport in general application scenarios at ∼25 °C. In this study, we develop novel bifunctional lithium salts with negative sulfonylimide (-SO 2 N(-)SO 2 -) anions mounted between two styrene reactive groups, which is capable of constructing 3D cross-linked networks with multiscale reticulated ion nanochannels, resulting in the uniform and rapid distribution of Li+ ions in the crosslinked electrolyte. To verify the feasibility of our strategy, we designed PVDF-HFP-based SICPEs and the obtained electrolyte exhibits high thermal stability, outstanding Li+ transference number (0.95), pleasing ionic conductivity (0.722 mS cm−1), and broad chemical window (greater than5.85 V) at ambient temperature. As a result of the electrolyte structural merits, the Li||LFP cells displayed excellent cycling stability (96.4% reversible capacities after 300 cycles at 0.2C) without additional auxiliary heating. This ingenious strategy is expected to providing a new perspective for advanced performance and high safety LMBs. [ABSTRACT FROM AUTHOR]