Electrochemical Performance of B‐Type Vanadium Dioxide as a Sodium‐Ion Battery Cathode: A Combined Experimental and Theoretical Study

Abstract

B‐type vanadium dioxide is a frequently investigated lithium‐ion battery material because of its appreciable gravimetric capacity, energy density, rate capability and cycling stability, but investigations of its performance with sodium working metal are scarce. We present a combined experimental‐theoretical study exploring the underlying mechanism of the electrochemical sodiation of B‐type vanadium dioxide. We find agreement between theoretical and experimental results, which complement each other and map out a detailed mechanistic picture. We are able to identify the sluggish diffusion of sodium ions in the vanadium dioxide host material, especially at low concentrations, as a key obstacle to the utilization of the pristine material as a high‐performance cathode for sodium‐ion batteries. Our findings provide context for previously reported results and can be used for a more targeted vanadium dioxide electrode design in the future.

Raman spectroscopy of Wadsley phases of vanadium oxide

“…11,12 In 1994, it was discovered that the LiMn 2 O 4 /VO 2 (B) couple represented the optimum electrode pair for the aqueous Li-ion cell. 24 Further applications of VO 2 (B) were developed after the discovery of synthesis routes to nanostructured samples and included electrochemistry (cathodes of Li-, [25][26][27] Na-, 28 and Al-ion 29 batteries, anodes for Li-, Na-, 30 and K-ion 31 batteries and supercapacitors 32,33 ), catalytic processes, 34 humidity, and liquefied petroleum gas sensors. 35,36 Strained VO 2 (B) thin films exhibited superior thermal sensitive properties and could be promising for uncooled IR detectors.…”

Advanced Vanadium Oxides for Sodium‐Ion Batteries

“…And a total gravimetric spesific capacity of 404 mAh g −1 would be achieved at ≈0.44 V, closing to the cyclic voltammetry (CV) result (≈0.52 V). [43] Shortly afterward, Fun et al proved that ≈1.24 Na + inserted into amorphous VO 2 (a-VO 2 ) with a superior specific capacity of over 400 mAh g −1 in the wide potential range of 1.0-4.0 V (vs Na/Na + ). Yet the corresponding crystalline VO 2 (c-VO 2 ) exhibited similar behaviour with the fully charged state to Na 1.10 VO 2 .…”

Recent progress in rate and cycling performance modifications of vanadium oxides cathode for lithium-ion batteries

“…The working principle of sodium-ion batteries (SIBs) is similar to that of lithium-ion batteries and the sodium reserves are abundant. Many vanadium oxides have been authenticated possessing sodium storage activity [103,[197][198][199]. For example, Huiying et al [200] synthesized nanocrystalline V 2 O 5 with bilayer structure as the cathode of SIBs, high capacity of 220 mAh/g (236 mAh/g for theoretical limit) was achieved and the retention was 92% after 500 cycles.…”