Practical implementation of next-generation Li-ion battery chemistries is to a large extent obstructed by the absence of an electrolyte that is capable of simultaneously supporting reversible electrochemical reactions at two extreme electrochemical potentials—above 4.5?V at the positive electrode and near 0?V vs. Li at the negative electrode. Electrolytes based on carbonate esters have been reliable in satisfying state-of-the-art Li-ion battery (LIB) chemistries below <4.2?V; however, it is the intrinsic thermodynamic tendency of these carbonates to decompose at potentials well below the thermodynamic threshold required for reversible reactions of high-voltage systems (>4.4?V), releasing CO2. In this work, we explore a carbonate-free electrolyte system based on a single sulfone solvent, in which a newly discovered synergy between solvent and salt simultaneously addresses the interfacial requirements of both graphitic anode and high-voltage cathode (LiNi0.5Mn1.5O4 (LNMO)). Experimental measurements, quantum chemistry (QC) calculations, and molecular dynamics simulations reveal the system’s fast ion conduction, stability over a wide temperature range, and non-flammability. At the anode, a LiF-rich interphase generated by early-onset reduction of the salt anion effectively suppresses solvent co-intercalation and subsequent graphite exfoliation, enabling unprecedented and highly reversible graphite cycling in a pure sulfone system. Under oxidative conditions, QC calculations predict that high salt concentration promotes complex/aggregate formation which slow the decomposition of sulfolane and leads to polymerizable rather than gaseous products—a fundamental improvement over carbonate solvents. These predictions are corroborated by X-ray photoelectron spectroscopy (XPS), cryogenic-transmission electron microscopy (TEM), and electron energy loss spectroscopy (EELS) experiments, which revealed the presence of a thin, conformal, sulfur-based cathode electrolyte interphase (CEI). Together, the functional interphases (SEI/CEI) generated by this electrolyte system supported long term operation of a high-voltage (4.85?V) LNMO/graphite full cell, which retained ~70% of its original first-cycle discharge capacity after the 1000th cycle. Based on these results, this new carbonate-free electrolyte system, supported by the mechanistic understanding of its behavior, presents a promising new direction toward unlocking the potential of next generation Li-ion battery electrodes.

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DOI: 10.1016/j.mattod.2018.02.005