Reaction Center Shifting in Partially Fluorinated Electrolytes for Robust Lithium Metal Battery

Abstract The strategic formulation of a compatible electrolyte plays a pivotal role in extending the longevity of lithium‐metal batteries (LMBs). Here, we present findings on a partially fluorinated electrolyte distinguished by a subdued solvation affinity towards Li + ions and a concentrated anion presence within the primary solvation layer. This distinctive solvation arrangement redirects the focal points of reactions from solvent molecules to anions, facilitating the predominant involvement of anions in the creation of a LiF‐enriched solid‐electrolyte interphase (SEI). Electrochemical assessments showcase effective Li + transport kinetics, diminished overpotential polarization for Li nucleation (28 mV), and prolonged cycling durability in Li||Li cells employing the partially fluorinated electrolyte. When tested in Li||NCM811 cells, the designed electrolyte delivers a capacity retention of 89.30 % and exhibits a high average Coulombic efficiency of 99.80 % over 100 cycles with a charge‐potential cut‐off of 4.6 V vs . Li/Li + under the current density of 0.4C. Furthermore, even at a current density of 1C, the cells maintain 81.90 % capacity retention and a high average Coulombic efficiency of 99.40 % after 180 cycles. This work underscores the significance of weak‐solvation interaction in partially fluorinated electrolytes and highlights the crucial role of solvent structure in enabling the long‐term stability and high‐energy density of LMBs.