Abstract Ether‐based electrolytes hold great promise for next‐generation lithium‐ion batteries (LIBs) owing to their low melting points and viscosities. However, their strong solvation ability promotes detrimental Li + ‐solvent co‐intercalation, leading to graphite exfoliation and limiting practical applications. Here, we employ topological structure engineering of ether solvents and demonstrate a synergistic mechanism of electronic effects (electropositivity defined by ESP max /electronegativity defined by ESP min ) and volume of solvent in modulating lithium storage behavior in graphite. We demonstrate that increased stability (as indicated by enhanced |ESP min | − ESP max ) and reduced volume of Li + ‐solvent complexes enhance the tendency for co‐intercalation. This necessitates the use of solvents featuring enriched base structures (─C 2 H 4 O─) and shorter terminal alkyl chain lengths (─C 2 H 4 ). Furthermore, we reveal that the primary cause of capacity decay during Li + ‐ether co‐intercalation processes is the continuous rupture and reformation of the solid electrolyte interphase (SEI). This work provides new insights into designing ether‐based electrolytes that compatible with graphite, paving a new way to develop high‐performance LIBs.
Chen et al. (2025) studied this question.