Iron-Vanadium Incorporated Ferrocyanides as Potential Cathode Materials for Application in Sodium-Ion Batteries

Abstract

Sodium-ion batteries (SIBs) are potential replacements for lithium-ion batteries owing to their comparable energy density and the abundance of sodium. However, the low potential and low stability of their cathode materials have prevented their commercialization. Prussian blue analogs are ideal cathode materials for SIBs owing to the numerous diffusion channels in their 3D structure and their high potential vs. Na/Na+. In this study, we fabricated various Fe-V-incorporated hexacyanoferrates, which are Prussian blue analogs, via a one-step synthesis. These compounds changed their colors from blue to green to yellow with increasing amounts of incorporated V ions. The X-ray photoelectron spectroscopy spectrum revealed that V3+ was oxidized to V4+ in the cubic Prussian blue structure, which enhanced the electrochemical stability and increased the voltage platform. The vanadium ferrocyanide Prussian blue (VFPB1) electrode, which contains V4+ and Fe2+ in the Prussian blue structure, showed Na insertion/extraction potential of 3.26/3.65 V vs. Na/Na+. The cycling test revealed a stable capacity of ~70 mAh g–1 at a rate of 50 mA g–1 and a capacity retention of 82.5% after 100 cycles. We believe that this Fe-V-incorporated Prussian green cathode material is a promising candidate for stable and high-voltage cathodes for SIBs.

Recent Advances in Sodium-Ion Batteries: Cathode Materials

“…Meanwhile, the presence of V-O binding in sodium vanadium hexacyanoferrate (NaVHCF) as a SIB cathode demonstrated only one redox potential [187]. Nguyen et al reported that the presence of V-O passivated the high-spin Fe related to the low redox potential, supporting the structure of the low-spin Fe ion; therefore, NaVHCF provided a single redox potential of approximately 3.26/3.65 V versus Na/Na + [192]. However, the capacity was only approximately 70-80 mAh g −1 .…”