Unravelling V<sub>6</sub>O<sub>13</sub> Diffusion Pathways <i>via</i> CO<sub>2</sub> Modification for High-Performance Zinc Ion Battery Cathode
Wen Shi, Bosi Yin, Yi Yan Yang, Michael B. Sullivan, John Wang, Yong‐Wei Zhang, Zhi Gen Yu, Wee Siang Vincent Lee, Junmin Xue
Abstract
Vanadium-based oxide is widely investigated as a zinc ion battery (ZIB) cathode due to its ability to react reversibly with Zn2+. Despite its successful demonstration, modification with simple molecules has shown some promise in enhancing the performance of ZIBs. Thus, this presents an immense opportunity to explore simple molecules that can dramatically improve the electrochemical performance of electrodes. Thus, the effect of CO2 modification is studied in this work by decomposing oxalic acid within a hydrated V6O13 framework. Based on the collective results, the presence of CO2 drastically lowers the relative energy of Zn2+ diffusion through the pathways by forming weak electrostatic interactions between OCO2 and Zn2+. This leads to an enlarged diffusion contribution, which consequently results in enhanced stability and better rate performance. The as-synthesized CO2–V6O13 electrode delivers one of the highest specific capacities reported for vanadium-based oxides of ca. 471 mAh g–1. Furthermore, an excellent cyclic stability of 80% capacity retention after 4000 cycles at 2 A g–1 is recorded for CO2–V6O13, which suggests the importance of simple molecules in the material framework toward the enhancement of ZIB cathode performance.