Designing High‐Performant Lithium Battery Electrolytes by Utilizing Two Natures of Li⁺ Coordination: LiTDI/LiTFSI in Tetraglyme

Abstract Highly concentrated electrolytes (HCEs) based on glymes, such as tetraglyme (G4), are currently the focus of much battery research, primarily due to their unique properties – especially with respect to ion transport and electrochemical stability. While the LiTFSI‐G4 and LiTDI‐G4 systems both have been studied extensively, we here design their hybrid electrolytes to answer; will the resulting properties be averages/superpositions or will there be synergies created? We find the latter to be true and demonstrate that the most performant electrolytes are obtained by introducing a minor amount of LiTDI to an LiTFSI based electrolyte, which promotes the disproportionation and formation of “free” cations and at the same to avoid large aggregates – shown comprehensively both experimentally and by different modelling approaches and analyses combined. This electrolyte composition strategy can be generalized to other salts and solvents and thus a route towards a flora of novel battery electrolytes is here suggested.