The Role of the Molecular Encapsulation Effect in Stabilizing Hydrogen‐Bond‐Rich Gel‐State Lithium Metal Batteries

Gel‐state polymer electrolytes with superior mechanical properties, self‐healing abilities and high Li+ transference numbers can be obtained by in situ polymerization of monomers with hydrogen‐bonding moieties. However, it is overlooked that the active hydrogen atoms in hydrogen‐bond donors experience displacement reactions with lithium metal in lithium metal batteries (LMBs), leading to corrosion of the lithium metal. Herein, it is discovered that the addition of hydrogen‐bond acceptors to hydrogen‐bond‐rich gel‐state electrolytes modulates the chemical activity of the active hydrogen atoms via the formation of hydrogen‐bonded intermolecular interactions. The characterizations reveal that the added hydrogen‐bond acceptors encapsulate the active hydrogen atoms to suppress the interfacial chemical corrosions of lithium metals, thereby enhancing the chemical stability of the polymer structure and interphase. With the employment of this strategy, a 1.1 Ah LiNi0.8Co0.1Mn0.1O2/Li metal pouch cell achieves stable cycling with 96.3% capacity retention at 100 cycles. This new approach indicates a feasible path for achieving in situ polymerization of highly stable gel‐state‐based LMBs.