Designing Localized High Concentration Electrolytes Based on Fluorinated Solvents for Lithium-Ion Batteries
Authors: Hossain Md Jamil , Wu Qisheng , Bock David C , Marschilok Amy C. , Takeuchi Kenneth J. , Takeuchi Esther S. , Qi Yue 
Published: September 2023

Reduction at the anode can affect electrolyte decomposition, solid electrolyte interphase (SEI) formation and growth, and thus the lithium solvation/de-solvation near the SEI, and ultimately lead to various perilous side reactions such as inactive lithium formation. Lithium ions solvated in the electrolyte solution along with salt anions diffuse towards the surface of the electrode. At the charged surface, these solvated ions can undertake different pathways leading to various reductive decomposition products to subsequently form the SEI. The transfer of electrons from the electrode to the salt anions form inorganic SEI products. The SEI layer gradually thickens during repeated charge/discharge cycles due to electron exposure to electrolyte or electrolyte diffusion to the anode surface. This gradual thickening of SEI layer decreases active lithium ions, solvents, and salts and increases cell resistance and lowers the cell capacity and Coulombic efficiency. Essentially, the choice of electrolytes has a significant influence on the formation of an SEI and its underlying chemical and mechanical properties. Optimizing the electrolytes is crucial for an SEI formation since the properties of the SEI significantly affect the lithium-ion batteries’ cyclability, life time, capacity retention, high power density, rate capability, and safety. One approach of stabilizing the SEI is to utilize an electrolyte with high concentration of salt, also known as High-Concentration Electrolytes (HCEs). This approach modifies the Li+ solvation structure to form contact ion pairs (CIP) and aggregates (AGG) while decreasing solvent-separated ion pairs (SSIPs) so that the salt anion, such as FSI-, is preferentially decomposed to form a robust LiF-rich SEI. LiF is considered a beneficial SEI component to block electron transport. By introducing a diluent (a non-solvating solvent) in the HCE to form Localized High Concentration Electrolyte (LHCE), the disadvantages of the HCE, such as low ionic conductivity, high viscosity and high cost, can be minimized while retaining the highly concentrated salt-solvent clusters as they are in the HCE. LHCEs based on fluorinated solvents and diluents can further stabilize the electrode-electrolyte interface. Recent studies showed that the presence of fluorine in the SEI, either in the form of simple inorganic fluorides (LiF) or organofluoro-moieties, brought positive impacts such as expanded electrochemical stability window and high ionic transport. Fluorinated solvents can shift the oxidation stability to a higher voltage compared to their nonfluorinated counterparts. Fluorinated electrolytes enable a high lithium plating Coulombic efficiency and suppresses lithium dendrite formation to a greater extent. In this work we focused on identifying the selection rules for the diluent for designing LHCEs to preserve or improve the local high salt concentration clusters to facilitate the formation of an inorganic rich anion derivative film on the anode as well as to enhance ionic conductivity to enable fast charging. Some of the important properties to consider while selecting a diluent are: - diluent molecules must offer little or no solubility to the salt so that they have minimal participation in the solvation clusters, they must be readily miscible with the solvating solvent so that they dissolve and remove some solvent molecules from the clusters; effectively increasing the salt concentration in the solvation clusters, diluents should be distributed on the periphery of salt-solvent clusters, diluents should have low viscosity, to reduce the overall viscosity of the formulated electrolyte, which in turn improves the ionic conductivity since the low viscosity of diluents allow for higher mobility of the ionic clusters. We analyzed LHCEs consisting of different diluents and diluent molar ratios in a comparative fashion to understand their properties in retaining or improving the structures of the high concentration salt-solvent clusters and improving ionic conductivity. We varied the diluent molar ratio to understand its relationship to increasing salt concentration gradients in the center of the solvent-salt clusters. We also analyzed the relationship between diluent molar ratio and ionic conductivity and found that an optimum diluent molar ratio exists for which the ionic conductivity can be maximized. Our findings serve as design guidelines for practical applications of LHCEs.