Challenges and Strategies of NASICON‐Type Solid‐State Electrolytes for High‐Performance Lithium Batteries

Owing to their high safety and energy density, all-solid-state batteries (ASSBs) are regarded as one of the most promising next-generation energy storage systems and have attracted significant attention. However, their large-scale deployment remains hindered by technical challenges, including interfacial issues between solid electrolytes and electrodes, dendrite growth, and poor cycling and rate performance. In particular, the limited ionic conductivity of solid electrolytes is widely regarded as one of the key factors constraining battery performance. Among them, NASICON-type solid electrolytes stand out as multifunctional oxide materials with rigid frameworks and excellent thermal stability, making them suitable for applications such as lithium-ion ASSBs. Nevertheless, they also face challenges of insufficient ionic conductivity and poor interfacial stability. This work reviews recent strategies to address these issues, conduct an in-depth analysis of its mechanism of action and effect, and evaluate its advantages, disadvantages, and development potential. To improve ionic conductivity, we discuss element doping, synthesis and fabrication methods, sintering additives, and densification strategies. To mitigate interfacial instability, we summarize approaches such as inorganic protective layers, composite electrolytes, and hot-pressing or hot-forming techniques. These insights provide both theoretical guidance and practical references for designing and developing high-performance, stable NASICON-type solid electrolytes.