Reconstructing Solvation Structure via Strongly Nucleophilic Anions for High‐Rate and Low‐Temperature Graphite||LFP Pouch Cells in PC‐Based Electrolyte

Regulating Li + solvation structure in Propylene carbonate (PC)‐based electrolytes modulates solid‐electrolyte interphase (SEI) formation and desolvation, enabling compatibility with graphite anodes. However, existing high‐ and localized high‐concentration strategies remain limited by cost and reduced ionic conductivity. Here, we report a nucleophilic‐anion‐regulated electrolyte that reconstructs the Li + solvation sheath without compromising transport. Through systematic simulations of six lithium salt anions, we reveal the role of in regulating Li + solvation. Introducing LiNO 3 salt enables partial replacement of solvent molecules in the first solvation shell with nucleophilic , decreasing solvent‐separated ion pairs by 26% while increasing contact ion pairs and aggregates by 19% and 7%, respectively. This solvation restructuring is experimentally validated, promoting Li + desolvation and forming a Li 3 N‐rich inorganic SEI, suppressing PC co‐intercalation and solvent decomposition. As a result, both Li||graphite half cells and high‐mass‐loading graphite||LiFePO 4 pouch cells exhibit markedly enhanced performance. The optimized electrolyte delivers nearly fourfold higher capacity at 3C and stable operation for over 100 cycles at −20°C, whereas cells with a control electrolyte fail within 20 cycles. This work establishes nucleophilic‐anion‐driven solvation regulation as a cost‐effective pathway for designing practical next‐generation electrolytes with fast‐ion transport, robust interfacial stability, and excellent low‐temperature performance.