Topological Structure Design of Ether Solvents for Lithium Storage Chemistry in Graphite Anode

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.