Harnessing Preferential Coordination of Ether in Electrolyte to Boost Oxidation Resistance for High‐Energy‐Density Lithium Metal Batteries

ABSTRACT Designing electrolyte capable of stabilizing electrode interfaces and regulating solvation structures to ensure efficient ion transport is critical for high‐energy lithium metal batteries (LMBs). However, conventional ether‐based electrolytes compatible with lithium metal anodes are limited by oxidative decomposition at high potential and high desolvation energy barriers. Here, we propose a preferential coordination strategy that reconstructs the Li + solvation structure by leveraging the Li + binding strength disparity among solvent molecules in ether‐siloxane hybrid electrolytes. In this approach, the high steric hindrance of substituents around the silicon atoms in siloxane solvents restricts their coordination distance with Li + . This guides the strongly coordinating ether solvents to preferentially form a stable solvation shell around Li + , reducing the concentration of free ether molecules prone to oxidative decomposition at high voltage. This anion‐rich solvation structure concurrently constructs a robust interphase and accelerates Li + desolvation. A 5.2 Ah LiNi 0.8 Co 0.1 Mn 0.1 O 2 || Li pouch cell based on the electrolyte demonstrates an energy density of 510.7 Wh kg −1 and maintains over 80% capacity retention after 100 cycles. The cell retains 356.7 Wh kg − 1 even at an extremely low temperature of −50°C. This work provides a generalizable electrolyte design principle for high‐voltage lithium metal battery by a solvent coordination engineering strategy.