Porous Crystalline Frameworks as Ion-Conducting Solid-State Electrolytes

Room-temperature Li⁺ conductors have been intensively revisited to develop high-safety solid-state batteries. While promising inorganic Li⁺ solid-state electrolytes (SSEs) with competitive ionic conductivity have been demonstrated, their practical applications are still hindered by manufacturing technology, cost constraints, and internal battery interfaces. Advances in the design and synthesis of periodic frameworks over the past decade have created a new platform for designing SSEs. These porous crystalline frameworks feature open channels that can be tailored into ion-hopping sites and guest-accessible voids, both essential for SSE construction. Framework-based SSEs uniquely merge the advantages of inorganic crystal-like ordered structures and the design flexibility of organic molecules, distinguishing them significantly from traditional inorganic or organic SSEs. Enhancing ionic conduction and exploring potential applications are two critical factors driving the rapid advancement of framework-based SSEs.