Zheng Ma, Yuehua Chen, Akang Huang, Jia Wang, Honghong Liang, Huan Yu, Zexu Wang, Pushpendra Kumar, Hongliang Xie, Qian Li, Jun Ming
Electrolyte–electrode interfacial modeling has emerged as a vital strategy to elucidate the intricate relationships among electrolyte solvation structure, desolvation dynamics, and electrode performance since 2018. This perspective summarizes the evolution of interfacial models from early anode-oriented systems to cathode-focused and ultimately integrated models incorporating weak intermolecular interactions and the solid electrolyte interphase (SEI). This holistic approach deepens the understanding of interfacial behavior and facilitates electrolyte design more effectively informed by solvation chemistry. We propose that the next frontier in electrolyte research lies in revealing the molecular and ionic interactions, electron delocalization states, and charge-transfer mechanisms at the electronic scale. Mechanistic understanding and control of these phenomena will enable the rational design of electrolyte components that regulate electron gain and loss, optimizing electrolyte functionality and electrochemical performance at the ampere-hour scale. Finally, we present a methodological roadmap toward this objective, establishing a robust foundation for next-generation functional electrolytes and high-performance batteries.