Efficient Screening of Electrolyte Additives for High‐Temperature, High‐Voltage Lithium Batteries via Fukui Functions

Abstract

Developing stable electrolytes for high‐voltage and high‐temperature lithium batteries remains a critical challenge due to severe interfacial degradation. This study presents a reactivity‐guided screening strategy based on density functional theory (DFT)‐derived Fukui functions to identify electrolyte additives that promote robust, inorganic‐rich electrode‐electrolyte interphases. Fukui function analysis achieves high prediction accuracy, outperforming conventional HOMO‐based screening, and demonstrates superior reliability in additive selection. By evaluating local electrophilic and nucleophilic reactivity, 4‐(Trifluoromethyl)thiobenzamide (TFSBN) is prioritized as a promising additive, with sulfur (S), fluorine (F), and nitrogen (N) sites facilitating oxidation. This, together with the preferential accumulation of TFSBN at the NCM811 interface, tailors the Li+ solvation structure and enables the formation of a robust inorganic‐rich electrode‐electrolyte interphase, suppressing transition metal dissolution and cathode cracking. Experimental validation reveals that TFSBN‐modified electrolyte (1TF) significantly enhances battery performance for high‐voltage (≥4.8 V) and high‐temperature (≥55 °C) operational conditions. The cell with 1TF also demonstrates exceptional fast‐charging stability and pouch cell compatibility. This work establishes a generalizable computational‐experimental framework for electrolyte additive design, accelerating the development of high‐energy‐density batteries under extreme operational conditions.