Recent advances in vanadium-based NASICON-structured cathode materials for sodium-ion batteries

Sodium-ion batteries (SIBs) are considered a promising alternative for large-scale energy storage due to the abundant sodium resources and low cost. NASICON-structured cathode materials are expected to achieve industrial production with their excellent structural stability, robust 3D diffusion channels, and high working voltage. Among them, vanadium-based NASICON cathodes stand out owing to their capability for multi-electron reactions, which are enabled by the accessible redox couples V³⁺/V²⁺ (∼1.6 V), V⁴⁺/V³⁺ (∼3.4 V), and particularly the high voltage V⁵⁺/V⁴⁺ (∼4.0 V vs. Na⁺/Na). First, this article introduces the fundamental structure of NASICON materials and their structure–property relationships. Thereafter, it comprehensively summarizes the recent progress in optimizing vanadium-based NASICON cathodes, focusing on key strategies including elemental doping, advanced synthesis techniques, surface coating/modification, activation of the high-voltage V⁵⁺/V⁴⁺ redox couple for enhanced capacity, exploitation of multi-electron reactions, and the emerging high-entropy design approach. Finally, based on the current challenges and research trends, this review outlines future research directions to advance the development of high-performance vanadium-based NASICON cathodes for practical SIB applications.