Mechanically Interlocked Networks Enable High‐Performance Propylene Carbonate‐Based Gel Electrolytes for Durable Lithium‐Ion Batteries

ABSTRACT Propylene carbonate (PC), with a wide liquid‐phase temperature range, represents an ideal electrolyte solvent for lithium‐ion batteries (LIBs) operating under extreme conditions. However, the strong Li + ‒PC coordination triggers severe solvent co‐intercalation of graphite anodes, leading to irreversible exfoliation and capacity decay. Herein, the mechanically interlocked network (MIN) is proposed to construct the gel polymer electrolyte (GPE) that effectively resolves this long‐standing incompatibility through a dual‐functional molecular design. The crown ether moieties within MIN establish dipole–dipole interactions with PC, disrupting the preferential Li + ‒PC coordination and thereby suppressing solvent co‐intercalation. The unique topological feature of MINs endows the gel host with high chain mobility, enabling rapid Li + transport that exceeds conventional GPEs. When integrated into 1 Ah‐level graphite||LiFePO 4 pouch cells, the MIN‐GPE (MGPE) with PC and LiPF 6 delivers improved cycling stability over 300 cycles and demonstrates reliable performance across a temperature range from −20°C to 30°C. Furthermore, MGPE exhibits favorable compatibility with high‐voltage LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes. This work highlights the potential of MINs as a versatile framework for GPE design to address PC incompatibility of graphite and sluggish Li + transport of the polymer host, offering new insights into the development of PC electrolytes for durable LIBs.