Agent molecule modulated low-temperature activation of solid-state lithium-ion transport for polymer electrolytes

Low-temperature activation of lithium-ion migration is crucial for enabling the practical application of solid-state polymer electrolytes for lithium-ion batteries. In this study, we perform a series of first-principle calculations and demonstrate that certain types of neutral molecules (so-called agent molecules) accelerate solid-state lithium-ion migration when mixed with lithium salts. We find that the intermolecular interaction in a selected agent-molecule/lithium-salt binary system is governed by the strong coupling between lithium and oxygen atoms. Upon the addition of agent molecules, the anionic species surrounding the lithium of lithium salts is replaced by the agent molecules. The resulting weakened Coulomb energy coupling between lithium and oxygen atoms is determined to be a key factor in enabling fast lithium-ion migration via facile dissociation of lithium salts and subsequent formation of ion-hopping sites in the form of lithium-free oxygen-cages. The structure-based interpretation of agent molecules suggests that neutral molecules with functional groups which enhance chemical resonance can be selected as potential agent molecules. We believe that the results obtained in this study serve as a theoretical basis for the future development of solid-state polymer electrolytes, particularly toward mitigating the dependence of lithium-ion transport on the movement of polymer chains. [Display omitted] •Certain types of neutral molecules accelerate solid-state lithium-ion transport.•Intermolecular interaction is governed by the strong lithium-oxygen coupling.•Anionic species surrounding the lithium are replaced by the neutral agent molecules.•Weakened lithium-oxygen coupling leads to the facile dissociation of lithium salts.•Formation of ion-hopping sites accelerates the lithium-ion migration.