Remodeling Highly Fluorinated Electrolyte via Shielding Agent Regulation toward Practical Lithium Metal Batteries

Abstract Highly fluorinated electrolytes have proved effective in improving electrochemical stability of lithium metal batteries. However, excessive fluorination not only detrimentally impacts the electrolyte ionic conductivity, but also inevitably forms the over‐fluorinated interphases with sluggish ion diffusivity. Herein, a strategy on remodeling Li + solvation structure in highly fluorinated electrolyte aided is proposed by fluorinated amide (FDMA), which denoted as “shielding agent”. Benefitting from FDMA's high donor number (DN) value (22.1), the Li + ‐dipole (fluoroethylene carbonate (FEC) or trans‐4,5‐Difluoroethylenecarbonate (DFEC)) interaction is interrupted and the participation of FDMA in primary solvation sheath fructify the solid‐electrolyte interphase without scarifying the privilege of fluorinated electrolyte on interphase chemistry. Eventually, the optimal high‐fluorinated electrolyte (FDMA/DFEC + 1.0 mol L −1 LiTFSI) with this unique shielding effect displays high ionic conductivity and rapid Li + desolvation behavior, enabling Li||LiNi 0.6 Co 0.2 Mn 0.2 O 2 (Li||NCM622) to achieve an ultralong cycle‐life of 2000 cycles at 1C with 84.7% capacity retention. Even under extreme conditions (NCM622: 10 mg cm −2 ; electrolyte: 20 µL; Li: 50 µm), the Li||NCM622 displays excellent electrochemical performance. Additionally, 447 Wh kg −1 Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (Li||NCM811) pouch cells have been successfully fabricated and demonstrate an exceptional cycle‐life over 150 cycles. The proposed “shielding” strategy to modulate the solvation structure paves the way for developing practical LMBs with fluorinated electrolytes.