A Hybrid Solvating Electrolytes Strategy for Rapid Li ⁺ Desolvation and High Ionic Conductivity Enabling Fast‐Charging and High‐Stability Lithium Metal Batteries

The development of fast‐charging lithium metal batteries (LMBs) is hindered by uncontrolled Li dendrite growth, unstable solid electrolyte interphase (SEI), and sluggish desolvation kinetics. Herein, we present a rational molecular design strategy for hybrid solvating electrolytes (HSEs) that integrates a weakly solvating sulfonamide (N, N‐dimethyl(trifluoromethanesulfonyl)amide, DMTMSA) with a strongly solvating fluoroethylene carbonate (FEC) and a dual‐salt system (LiTFSI/LiDFOB). Unlike conventional single‐solvent systems, this unique combination creates an anion‐dominated primary solvation sheath, which thermodynamically weakens the Li +– solvent binding and kinetically reduces both the charge‐transfer barrier at the electrode interface and the Li + migration barrier within the SEI, ultimately enabling fast interfacial ion transport kinetics. Eventually, the electrolyte with this unique solvation structure (DMTMSA/FEC + LiTFSI/LiDFOB) exhibits high ionic conductivity (7.78 mS cm −1 ) and rapid Li + desolvation, enabling a LiNi 0.8 Co 0.1 Mn 0.1 O 2 (Li||NCM811) to achieve an extended cycle life of 350 cycles at 1C with a capacity retention of 78.8%. Additionally, a 2 Ah Li||NCM811 pouch cell is successfully fabricated and demonstrates excellent cyclability exceeding 100 cycles. Therefore, this rational design concurrently achieves fast‐charging capability and high stability in high‐energy‐density lithium metal batteries, paving a new avenue for electrolyte development.