Kao Chun-Chuan, Ye Chao, Hao Junnan, Shan Jieqiong, Li Huan, Qiao Shi-Zhang
School of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA5005, Australia.
ACS Nano. 2023 Feb 28;17(4):3948-3957. doi: 10.1021/acsnano.2c12587. Epub 2023 Feb 6.
Aqueous Zn-ion batteries hold practical promise for large-scale energy storage because of the safety and affordability of aqueous-based electrolytes; in addition, the manufacturing process is significantly simplified by direct employment of Zn metal as an anode. However, hydrogen evolution due to near-surface water dissociation has hindered large-scale applications of them. Here, we report the suppression of the hydrogen evolution reaction via a CuN-coordinated graphitic carbonitride (CuN-CN) anticatalytic interface to achieve highly efficient aqueous Zn-ion batteries. Based on gas chromatography and synchrotron-based X-ray diffraction spectroscopy, we demonstrated that the hydrogen evolution reaction triggers the ZnSO(OH)·HO formation. A combination of infrared spectroscopy and density functional theory simulations has proved to stabilize near-surface HO species and regulate adsorption of H* intermediates by an anticatalytic interface for hydrogen evolution reaction suppression. Consequently, the anticatalytic interface greatly improves the Coulombic efficiency of Zn plating/stripping to ∼99.7% for 5500 cycles and the cycling reversibility to over 1300 h at 1 mA cm and 1 mAh cm. With an anticatalytic interface, the full cell shows an excellent Coulombic efficiency of 98.3% over 400 cycles at 1C. These findings provide strategic insight for targeted designing of highly efficient aqueous Zn-ion batteries.
水系锌离子电池因其水系电解质的安全性和成本效益，在大规模储能方面具有实际应用前景；此外，直接使用锌金属作为阳极可显著简化制造工艺。然而，近表面水离解导致的析氢反应阻碍了它们的大规模应用。在此，我们报道了通过CuN配位的石墨相氮化碳（CuN-CN）反催化界面抑制析氢反应，以实现高效水系锌离子电池。基于气相色谱和同步辐射X射线衍射光谱，我们证明析氢反应触发了ZnSO(OH)·H₂O的形成。红外光谱和密度泛函理论模拟相结合，证明了通过反催化界面稳定近表面H₂O物种并调节H*中间体的吸附，从而抑制析氢反应。因此，反催化界面极大地提高了锌电镀/剥离的库仑效率，在5500次循环中达到约99.7%，在1 mA cm⁻²和1 mAh cm⁻²条件下循环可逆性超过1300小时。具有反催化界面的全电池在1C下400次循环中显示出98.3%的优异库仑效率。这些发现为高效水系锌离子电池的靶向设计提供了战略见解。
