Thermodynamic and Kinetic Behaviors of Electrolytes Mediated by Intermolecular Interactions Enabling High-Performance Lithium-Ion Batteries

作者：Hongliang Xie, Haoran Cheng, Pushpendra Kumar, Yuqi Wang, Honghong Liang, Tao Cai, Fei Zhao, Z. Cao, Luigi Cavallo, Zheng Ma, Qian Li, Jun Ming · 发表于：ACS Nano · 年份：2024 · DOI：10.1021/acsnano.4c07986 · 被引用次数：77 · 研究领域：Advancements in Battery Materials、Advanced Battery Materials and Technologies、Advanced Battery Technologies Research

Electrolyte solvation chemistry regulated by lithium salts, solvents, and additives has garnered significant attention since it is the most effective strategy for designing high-performance electrolytes in lithium-ion batteries (LIBs). However, achieving a delicate balance is a persistent challenge, given that excessively strong or weak Li + -solvent coordination markedly undermines electrolyte properties, including thermodynamic redox stability and Li + -desolvation kinetics, limiting the practical applications. Herein, we elucidate the crucial influence of solvent–solvent interactions in modulating the Li + -solvation structure to enhance electrolyte thermodynamic and kinetic properties. As a paradigm, by combining strongly coordinated propylene carbonate (PC) with weakly coordinated cyclopentylmethyl ether (CPME), we identified intermolecular interactions between PC and CPME using 1 H– 1 H correlation spectroscopy. Experimental and computational findings underscore the crucial role of solvent–solvent interactions in regulating Li + -solvent/anion interactions, which can enhance both the thermodynamic (i.e., antireduction capability) and kinetic (i.e., Li + -desolvation process) aspects of electrolytes. Additionally, we introduced an interfacial model to reveal the intricate relationship between solvent–solvent interactions, electrolyte properties, and electrode interfacial behaviors at a molecular scale. This study provides valuable insights into the critical impact of sol...