Yin Jiayi, Luo Yuzhe, Li Meng, Wu Meifen, Guo Kunkun, Wen Zhaoyin
College of Materials Science and Engineering, Hunan University, Changsha 410082, P. R. China.
CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, P. R. China.
ACS Appl Mater Interfaces. 2024 Oct 2;16(39):53242-53251. doi: 10.1021/acsami.4c11404. Epub 2024 Sep 23.
Rechargeable aqueous Zn-ion batteries (AZIBs) have been recognized as competitive devices for large-scale energy storage due to their characteristics of low cost, safe operation, and environmental friendliness. Nevertheless, their practical applications are greatly limited by zinc dendrite growth and side reactions occurring at the anode/electrolyte interface. Herein, we propose an effective and simple electrolyte engineering strategy, which is the introduction of l-lysine additive containing two amino groups and one carboxyl group into a ZnSO electrolyte to achieve stable and reversible Zn depositions. Theoretical calculations and experimental results reveal that the l-lysine can adsorb on the Zn anode surface due to the strong coordination effects between amino groups and Zn metal (Zn-N binding) and induce the reduction of ZnSO into inorganic ZnS, which can not only prevent interfacial side reactions but also regulate interfacial electric field on the zinc electrode surface to guide uniform Zn electrodeposition to inhibit zinc dendrites. Consequently, the l-lysine additive in the electrolyte enables Zn||Zn symmetric cells to achieve an ultralong stable cycling up to 2400 h at 1 mA cm with a low polarization of only about 16 mV and Zn||Cu asymmetric cells to obtain a high average Coulombic efficiency of 99.80% after stably cycling for more than 2000 h at 2 mA cm (1 mAh cm). In addition, the Zn||MnO@CNT full cell in an l-lysine-containing electrolyte also exhibits good cycling performance. This study offers a new perspective on multifunctional electrolyte additive for achieving highly reversible Zn metal anodes in AZIBs.
可充电水系锌离子电池(AZIBs)因其成本低、运行安全和环境友好等特性,已被公认为是大规模储能的具有竞争力的器件。然而,它们的实际应用受到锌枝晶生长以及阳极/电解质界面处发生的副反应的极大限制。在此,我们提出一种有效且简单的电解质工程策略,即将含有两个氨基和一个羧基的L-赖氨酸添加剂引入ZnSO电解质中,以实现稳定且可逆的锌沉积。理论计算和实验结果表明,由于氨基与锌金属之间的强配位作用(Zn-N键合),L-赖氨酸可以吸附在锌阳极表面,并促使ZnSO还原为无机ZnS,这不仅可以防止界面副反应,还能调节锌电极表面的界面电场,以引导均匀的锌电沉积,从而抑制锌枝晶。因此,电解质中的L-赖氨酸添加剂使Zn||Zn对称电池在1 mA cm下能够实现长达2400 h的超长稳定循环,极化仅约16 mV,并且使Zn||Cu不对称电池在2 mA cm(1 mAh cm)下稳定循环超过2000 h后获得99.80%的高平均库仑效率。此外,含L-赖氨酸的电解质中的Zn||MnO@CNT全电池也表现出良好的循环性能。这项研究为在AZIBs中实现高度可逆的锌金属阳极的多功能电解质添加剂提供了新的视角。