Amorphous VO₂: A Pseudocapacitive Platform for High‐Rate Symmetric Batteries

Abstract Among the various VO₂ polymorphs, the layered compound, VO₂(B), has been the most widely investigated lithium‐ion battery electrode material. For sodium‐ion electrodes, however, an amorphous solid may be more advantageous as a result of the open framework to facilitate ion insertion and the ability to tolerate volumetric changes. Herein, it is shown that the Na⁺ insertion properties of amorphous VO₂ (a‐VO₂) are superior to those of crystalline VO₂(B). Amorphous VO₂ exhibits a linear voltage characteristic over a 3 V range (4.0 to 1.0 V vs Na/Na⁺) leading to a reversible capacity as high as 400 mAh g⁻¹ and rapid redox kinetics, which is attributed to its pseudocapacitive nature. The linear voltage characteristic over 3 V affords the opportunity of fabricating a symmetric Na‐ion battery in which the a‐VO₂ material serves as both the positive electrode and the negative electrode. Such a symmetric battery offers safer operation in terms of overcharging, overdischarging, polarity reversal, high charge/discharge current abuse, and long‐term usage. The results suggest that amorphous transition metal oxides may offer advantageous attributes for rapid, safe, and energy‐dense storage.