Abstract: Owing to its high theoretical capacity (3860 mAh/g, over 10 times that of graphite) and its lowest theoretical electrochemical potential (-3.04 V vs SHE), Li metal is an ideal anode material for improving the capacity of rechargeable Li batteries [1]. However, the practical application of the Li anode is severely hindered by its high reactivity with standard electrolyte compositions, which results in limited Coulombic efficiency (CE) in those electrolytes (for instance, 85-90% with 1 M LiPF 6 EC:DEC [2]). Strategies to improve CE have focused on electrolyte engineering, including development of highly concentrated electrolytes (HCE) and more recently, local high-concentration electrolytes (LHCE) [3] . A feature shared by these strategies is the promotion of contact-ion pairing, which enhances anion contributions to the solid electrolyte interphase (SEI). Among the best-performing salts are fluorinated lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), which are believed to promote stable inorganic-rich SEIs and correlate with higher CE [4]. A second strategy of interest is to pu rsue development of additives incorporated at relatively low concentrations ( e.g. , 2-5 wt%) that can favorably alter the SEI, such as carbonates ( e.g. , vinylene carbonate (VC) [5] and fluoroethylene carbonate (FEC) [6] ), sulfates ( e.g. , ethylene sulfate (DTD) and 1,3-propanesulfonate (PS) [7]), and borates ( e.g. , lithium difluoro(oxoalate) borate (LiDFOB) [8] and tris (2,2,2-trifluoroethyl) borate (TTFEB) [9] ). An advantage of this strategy is the possibility to ultimately lower reliance on high fluorinated salt concentrations, which are costly and can be corrosive towards the Al current collector, and potentially expand the versatility of available electrolyte frameworks having competitive CE. However, compared to the principles developed for salt and solvent selection in HCE and LHCE, the mechanism behind successful additive activation needs elucidation. In this work, we examined the potential of "FSI-like," neutral sulfonyl/sulfamoyl fluorides (R-SO 2 F and R-R’-NSO 2 F, Figure 1) as functional additives for Li cycling, motivated by their structural similarity to the high-performance FSI - anion. The examined baseline electrolytes include high-CE systems consisting of LiFSI dissolved in various solvents: fluoroethylene carbonate (FEC, 1 and 4 M salt), 1,2-dimethoxyethane (DME, 4 M), and dimethyl carbonate (DMC, 6 M). The ability for each additive to coordinate with Li + was first examined by NMR, with trends rationalized in part by supporting microcalorimetry data on the degree of solvent coordination strength. We relate these to CE and cycling outcomes in each electrolyte. Interestingly, we find that additives have negligible effect on CE in FEC-based electrolytes, whereas significant impacts were observed in DME and DMC. We relate these diverse outcomes to the SEI chemical compositions and gases evolved during galvanostatic cycling, as characterized by X-ray photoelectron spectroscopy (XPS) and gas chromatography (GC), which help to rationalize competitive reactions among solvent, anion, and additive. Unfortunately, additives had a negative-to-neutral impact on CE in these systems. Thus, we finally examined a LiPF 6 in carbonate electrolyte, 1 M LiPF 6 in EC/DMC (LP40), where we hypothesized that competitive reduction of coordinating additives over problematic carbonate solvent would lead to performance gains. Indeed, significant improvements (up to 94%, compared to baseline 89% over the initial 50 cycles) in CE were observed for two additives, with their structural advantages further discussed. Overall, our findings provide insights into the effects of sulfonyl/sulfamoyl fluoride additive structures on Li metal cyclability and the compositions of baseline electrolytes whose electrochemical cycling stability can be effectively modulated by these additives. Xu, W., et al., Lithium metal anodes for rechargeable batteries. Energy & Environmental Science, 2014. 7 (2):p.513-537. Genovese, M., et al., Combinatorial methods for improving lithium metal cycling efficiency. Journal of The Electrochemical Society, 2018. 165 (13):p.A3000. Hobold, G.M., et al., Moving beyond 99.9% Coulombic efficiency for lithium anodes in liquid electrolytes. Nature Energy, 2021. 6 (10):p.951-960. Suo, L., et al., Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries. Proceedings of the National Academy of Sciences, 2018. 115 (6):p.1156-1161. Aurbach, D., et al., On the use of vinylene carbonate (VC) as an additive to electrolyte solutions for Li-ion batteries. Electrochimica acta, 2002. 47 (9):p.1423-1439. Markevich, E., et al., Fluoroethylene carbonate as an important component in electrolyte solutions for high-voltage lithium batteries: role of surface chemistry on the cathode. Langmuir, 2014. 30 (25):p.7414-7424. Han, B., et al., Poor Stability of Li2CO3 in the Solid Electrolyte Interphase of a Lithium ‐Metal Anode Revealed by Cryo ‐Electron Microscopy. Advanced Materials, 2021. 33 (22):p.2100404. Liu, J., et al., Lithium difluoro (oxalato) borate as a functional additive for lithium-ion batteries. Electrochemistry communications, 2007. 9 (3):p.475-479. Ma, Y., et al., Enabling reliable lithium metal batteries by a bifunctional anionic electrolyte additive. Energy Storage Materials, 2018. 11 :p.197-204. Figure 1. (a) Sulfonyl/sulfamoyl fluoride chemical structures and (b) R-S and S-F bond lengths calculated by density functional theory. Figure 1