Computational Study of Li+ Solvation Structures in Fluorinated Ether, Non-Fluorinated Ether, and Organic Carbonate-Based Electrolytes at Low and High Salt Concentrations

Understanding the solvation structure of electrolytes is crucial for optimizing the performance and stability of lithium-ion batteries. Novel solvents are essential for enhancing electrolyte structure and ensuring better integration with modern electrode systems. However, there are limited studies focused on fluorinated solvent-based electrolytes. Herein, we report a new weakly solvated ether electrolyte (WSEE) composed of a pure fluorinated ether solvent, which results in an anion-rich solvation structure even at a low salt concentration of 1M. To explore this, we selected the advanced fluorinated solvent 2,2-Difluoroethyl Methyl Ether (FEME) and compared it with Dipropyl Ether (DPE), Ethylene Carbonate (EC), and Diethyl Carbonate (DEC). The prepared electrolyte systems include DPE with 1M, 1.8M, and 4M LiFSI, FEME with 1M, 1.8M, and 4M LiFSI, and a 1:1 vol% EC/DEC mixture containing 1M LiPF6. In this work, we comprehensively investigate the Li+ solvation structures in these electrolytes using Molecular Dynamics (MD) simulations and Density Functional Theory (DFT) calculations. Our computational findings indicate the presence of large ion aggregates (AGGs) in each DPE- and FEME-based electrolyte, while SSIPs (68%) are the dominant species in the mixed EC/DEC electrolyte. Notably, the formation of large ion aggregates is more pronounced in FEME-based electrolytes. We find that, similar to DPE, FEME solvent also exhibits weak solvating power across all examined salt concentrations. Furthermore, the quantum mechanical features of the Li+ solvation structures in DPE+1.8M LiFSI, FEME+1.8M LiFSI, and EC/DEC+1M LiPF6 electrolytes have been analyzed in detail using DFT calculations. We anticipate that this study will provide valuable insights into the Li+ solvation structures in DPE, FEME, and EC/DEC electrolytes, where the ether-based electrolytes exhibit closely similar properties.
Comment: For the associated GIF file, see: https://github.com/mana121/SolvationStructure/blob/main/results/previewGIF.md