The Role of Ion-Polaron Electrostatic Attraction on Zn2+ Migration in α-V2O5 for Zinc Ion Battery: Insights from First-Principles Calculations

作者：Yiming Guo, Dan Wu, Zhuo Sun, Fanghua Ning, Kai Zhu, Xiaoyu Liu, Shigang Lu, Yongyao Xia, Yi Jin · 发表于：The Journal of Physical Chemistry Letters · 年份：2025 · DOI：10.1021/acs.jpclett.4c03359 · 被引用次数：6 · 研究领域：Advanced battery technologies research、Transition Metal Oxide Nanomaterials、Supercapacitor Materials and Fabrication

The migration of Zn 2+ ions is significantly more challenging compared to that of Li + ions within the same crystalline framework, leading to poor rate performance of zinc-ion batteries (ZIBs). Compared to Li +, the slower migration rate of Zn 2+ is vaguely attributed to the stronger electrostatic interaction induced by Zn 2+ . Herein, the rule of how the size of the migration channel and electrostatic interaction affect Zn 2+ and Li + migration in α-V 2 O 5 has been systematically investigated by first-principle calculations. It is found that expanding the layer spacing can facilitate Zn 2+ migration. Once the layer spacing surpasses a certain threshold, further expansion does not lead to a continued reduction in the migration barrier. The local structure distortions caused by electron small polarons would lead to a decrease in migration channel size, which should have increased the energy barrier for Li + and Zn 2+ migration. However, interestingly, the electron small polarons decrease the energy barriers, which would be attributed to the ion-polaron electrostatic attraction. The higher activation barriers for the migration of Zn 2+ ions compared to those of Li + ions can be rationalized by the specific ion-polaron electrostatic attraction for Zn 2+ . Moreover, the comparative strength of the polaron-ion electrostatic attraction for alkali and alkaline earth metal ions is unveiled. Overall, this study provides theoretical insights into the role of ion-polaron electrostatic ...