Li Chang, Song Yang, Gao Ning, Ye Can, Xu Xuebing, Yang Weisheng, Hu Chaoquan
Zhongke Nanjing Institute of Green Manufacturing Industry, Nanjing, Jiangsu 211135, P. R. China.
State Key Laboratory of Mesoscience and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, P. R. China.
ACS Appl Mater Interfaces. 2024 May 15;16(19):24612-24623. doi: 10.1021/acsami.4c02476. Epub 2024 May 6.
Interfacial active water molecule-induced parasitic reactions and stochastic Zn transport-caused dendrite issue significantly impede the implementation of aqueous Zn-ion batteries. Herein, three positively charged amino acids, namely arginine, histidine, and lysine, were utilized as adsorption-type electrolyte additives to enhance the stability and reversibility of Zn anodes. Combined theoretical and experimental analyses verified that these amino acid cations can synergistically modulate the interfacial microenvironment and promote orientational Zn deposition. The adsorbed amino acid cations reconfigured the interfacial electric double layer structure, forming SO- and HO-poor interfaces, thereby retarding hydrogen evolution and corrosion side reactions. Simultaneously, the preferential adsorption of the amino acid cations at specific facets induced crystallographic orientational Zn deposition along unterminated facets. Three deposition architectures, namely planar texture, subvertical alignment, and vertical erection, were obtained, all effectively inhibiting dendrite formation. Consequently, symmetric cells with the three amino acid cations exhibited high stripping/plating reversibility of over 2000 cycles at 5 mA cm. Moreover, MnO-based full cells exhibited markedly improved stabilities compared with their additive-free counterparts.
界面活性水分子引发的寄生反应以及随机锌传输导致的枝晶问题严重阻碍了水系锌离子电池的应用。在此,精氨酸、组氨酸和赖氨酸这三种带正电荷的氨基酸被用作吸附型电解质添加剂,以提高锌负极的稳定性和可逆性。理论与实验相结合的分析证实,这些氨基酸阳离子能够协同调节界面微环境并促进锌的定向沉积。吸附的氨基酸阳离子重构了界面双电层结构,形成了贫硫酸根离子和贫氢氧根离子的界面,从而抑制析氢和腐蚀副反应。同时,氨基酸阳离子在特定晶面的优先吸附诱导了沿未终止晶面的晶体学取向锌沉积。获得了三种沉积结构,即平面纹理、亚垂直排列和垂直直立,均有效抑制了枝晶形成。因此,含有这三种氨基酸阳离子的对称电池在5 mA cm下表现出超过2000次循环的高剥离/电镀可逆性。此外,与无添加剂的MnO基全电池相比,含添加剂的全电池稳定性显著提高。