Structure designing, interface engineering, and application prospects for sodium‐ion inorganic solid electrolytes

Abstract All‐solid Na‐ion batteries (ASNIBs) present significant potential for integration into large‐scale energy storage systems, capitalizing on their abundant raw materials, exemplary safety, and high energy density. Among the pivotal components propelling the advancement of ASNIBs, inorganic solid electrolytes (ISEs) have garnered substantial attention in recent years due to their high ionic conductivity ( σ ), wide electrochemical stability window (ESW), and high shear modulus. Herein, this review systematically encapsulates the latest strides in Na‐ion ISEs, furnishing a comprehensive panorama of various ISE systems along with their interface engineering strategies against the electrodes. The prime focus resides in accentuating key strategies for refining ion conduction properties and interfacial compatibility of ISEs through structure design and interface modification. Furthermore, the review explores the foremost challenges and prospects inherent to sodium‐ion ISEs, striving to deepen our understanding of how to engineer more robust and efficient ISEs and interface stability, poised for the forthcoming era of advanced ASNIBs.