Enabling the Operation of Highly Compatible LiI‐3‐Hydroxypropionitrile Small‐Molecule Solid‐State Electrolytes in Lithium Metal Batteries via Stepped‐Amorphization Strategy

Abstract Integrating the advantages of both inorganic ceramic and organic polymer solid‐state electrolytes, small‐molecule solid‐state electrolytes represented by LiI‐3‐hydroxypropionitrile (LiI‐HPN) inorganic–organic hybrid systems possess good interfacial compatibility and high modulus. However, their lack of intrinsic Li + conduction ability hinders potential application in lithium metal batteries until now, despite containing LiI phase composition. Herein, inspired by evolution tendency of ionic conduction behaviors together with first‐principles molecular dynamics simulations, we propose a stepped‐amorphization strategy to break the Li + conduction bottleneck of LiI‐HPN. It involves three progressive steps of composition (LiI‐content increasing), time (long‐time standing), and temperature (high‐temperature melting) regulations, to essentially construct a small‐molecule‐based composite solid‐state electrolyte with intensified amorphous degree, which realizes efficient conversion from an I − to Li + conductor and improved conductivity. As a proof, the stepped‐optimized LiI‐HPN is successfully operated in lithium metal batteries cooperated with Li 4 Ti 5 O 12 cathode to deliver considerable compatibility and stability over 250 cycles. This work not only clarifies the ionic conduction mechanisms of LiI‐HPN inorganic–organic hybrid systems, but also provides a reasonable strategy to broaden the application scenarios of highly compatible small‐molecule solid‐state electrolytes.