Hierarchically Porous Vanadium-Based Cathode Materials for High-Performance Na-Ion Batteries

Sodium-ion batteries (SIBs) have emerged as a promising alternative to lithium-ion batteries (LIBs) in sectors requiring extensive energy storage. The abundant availability of sodium at a low cost addresses concerns associated with lithium, such as environmental contamination and limited availability. However, SIBs exhibit lower energy density and cyclic stability compared to LIBs. One of the key challenges in improving the performance of SIBs lies in the electrochemical properties of the cathode materials. Among the various cathodes utilized in SIBs, sodium vanadium phosphates (NVPs) and sodium vanadium fluorophosphates (NVPFs) are particularly advantageous. These vanadium-based cathodes offer high theoretical capacity and are cost-effective. Commercialization of SIBs with NVPF cathodes has already begun. However, the poor conductivity of these cathode materials leads to a short cycle life and inferior rate performance. Various synthesis methods have been explored to enhance the conductivity, including heteroatom doping (N, S, and Co), surface modification, the fabrication of porous nanostructures, and composite formation with conductive carbon materials. In particular, cathodes with interconnected hierarchical micro- and nano-porous morphologies have shown promise. This review focuses on the diverse synthesis methods reported for preparing hierarchically porous cathodes. With increased attention, particular emphasis has been placed on carbon composites of NVPs and NVPFs. Additionally, the synthesis of vanadium pentoxide-based cathodes is also discussed.