Dilute electrolyte with chaotropic anion addition for enhanced Zn-Ion storage performance in MXenes
Liping Zhang, Leiqiang Qin, Yeying Li, Le Du, Manting Song, Y. Wang, Jingkun Xu, Baoyang Lu, Johanna Rosén, Jianxia Jiang
Abstract
Optimizing electrolytes is essential for improving the electrochemical stability window (ESW) and energy storage capacity of aqueous energy storage devices. High-concentration electrolytes improve performance but face solubility, conductivity, and stability issues. Here, a strong chaotropic anion, ClO 4 − , is introduced into 1 M ZnSO 4 to expand the ESW and boost performance in dilute electrolytes. Theoretical simulation and experimental results provide that perchlorate not only significantly enhances ionic conductivity, leading to faster ion diffusion, but also weakens hydrogen bonds formation, reduces free water at the electrode surface, and promote the desolvation of hydrated zinc ions. Collectively, these factors lead to an improvement in the ESW and enhance overall device performance. Therefore, in the mixed electrolyte of 0.005 M Zn(ClO 4 ) 2 and 1 M ZnSO 4 , the Zn//Mo 2 ScC 2 T z aqueous zinc-ion hybrid supercapacitor (ZHSC) achieves a voltage window expansion from 1.0 to 1.3 V, delivering a high specific capacitance of 692.3 F g −1 at 0.2 A g −1 . Furthermore, an asymmetric supercapacitor with the same electrolyte operates at 1.8 V, delivering an energy density of 98.1 Wh kg −1 at 180 W kg −1 and maintaining 17 Wh kg −1 at 9000 W kg −1 . Notably, this electrolyte design strategy is universally applicable for enhancing Zn-ion storage performance of MXene-based materials. The effect of chaotropic anion on the electrochemical stability window and Zn-ion storage capacity in dilute electrolytes is investigated. Incorporating perchlorate into 1 M ZnSO 4 significantly weakened the hydration of zinc ions, enhanced the desolvation effect, and suppressed hydrogen evolution, thus improving electrochemical performance. Furthermore, this electrolyte design strategy is universally applicable for enhancing Zn-ion storage performance of MXene-based materials.