Molecular Engineering of Non‐Covalent Networks in Multi‐Functional Gel Electrolytes for High‐Performance Solid‐State Li─O ₂ Batteries

ABSTRACT The persistent challenges of sluggish redox kinetics in lithium‐oxygen batteries (LOBs) necessitate the exploration of active and compatible solid‐state electrolytes (SSEs). Herein, we report a multi‐functional gel polymer electrolyte (denoted as PGFEN) with well‐defined functional groups through ring‐opening reaction in the polymerized glycidyl methacrylate/2,2,3,4,4,4‐hexafluorobutyl acrylate electrolyte (PGFE) induced by N‐containing groups, to provide non‐covalent interaction networks toward stable ultra‐low overpotential solid‐state LOBs. Concretely, the molecular‐level micro‐environment facilitates the dissociation of Li‐TFSI and alters the solvation structure via the Li/H bond, thus enabling an ionic conductivity of 0.22 mS cm ⁻¹ . Moreover, the polar oxygen/nitrogen sites within multiple functional groups dynamically break the symmetry and stability of Li ₂ O ₂ and accelerate the redox kinetics via non‐covalent interactions, as evidenced by the theoretically elongated bond length and lowered Mayer bond order of Li─O bonds, thus reducing discharge/charge overpotential to 0.56 V for 100 cycles, and delivering an ultrahigh discharge capacity of 31718 mAh g ⁻¹ at 500 mA g ⁻¹ . Importantly, the smooth operations of a pouch‐type LOB for 70 cycles and a Li−air battery for 400 h demonstrate the great potential in practical application. This work opens new avenues using non‐covalent interactions to create efficient and stable SSEs for advancing the rapid development of LOBs.