In Situ Species Analysis of a Lithium-Ion Battery Electrolyte Containing LiTFSI and Propylene Carbonate.

In this study, we analyzed the species in a model electrolyte consisting of a lithium salt, lithium bis(trifluoromethane sulfone)imide (LiTFSI), and a widely used neutral solvent propylene carbonate (PC) with excess infrared (IR) spectroscopy, ab initio molecular dynamics simulations (AIMD), and quantum chemical calculations. Complexing species including the charged ones [Li + (PC) 4 , TFSI - , TFSI - (PC), TFSI - (PC) 2 , and Li(TFSI) 2 - ] are identified in the electrolyte. Quantum chemical calculations show strong Li + ···O(PC) interaction, which suggests that Li + would transport in the mode of solvation-carriage. However, the interaction energy of each hydrogen bond in TFSI - (PC) is very weak, suggesting that TFSI - would transport in hopping mode. In addition, the concentration dependences of the relative population of the species were also derived, providing a scenario for the dissolving process of the salt in PC. These in-depth studies provide physical insights into the structural and interactive properties of the electrolyte of lithium-ion batteries.