Lu Wang, Huaming Yu, Dongping Chen, Youliang Jin, Liangliang Jiang, Hanwei He, Gang Zhou, Zeqiang Xie, Yuejiao Chen
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引用次数: 0
摘要
锌金属具有优异的理论容量、惊人的能量密度和较低的氧化还原电位,是一种前景广阔的阳极材料。然而,锌枝晶生长、阳极腐蚀以及在水性电解质中的副反应等挑战极大地阻碍了锌金属阳极的实际应用。本文引入了 3-(1-吡啶)-1-丙磺酸盐(PPS)作为齐聚物添加剂,以实现锌的长期和高度可逆的电镀/剥离。PPS 添加剂具有π-π共轭吡啶阳离子和磺酸阴离子的强配位能力,在电场力的作用下会发生取向极化,从而产生动态吸附层,形成独特的贫水界面。具有立体阻碍效应和强配位能力的 PPS 可以吸引溶解的 Zn2+,从而促进脱溶过程。此外,通过提供大量成核位点和诱导锌离子流动,可实现 (002) 晶面的优选取向。因此,界面电化学还原动力学得到了调节,并确保了锌的均匀沉积。由于这些优点,含有 PPS 添加剂的 Zn//Zn 对称电池表现出显著的循环稳定性,超过 2340 小时(1 mA cm-2 和 1 mA h cm-2)。此外,Zn//V2O5 全电池的稳定循环时间也长达 6000 个循环。
Steric hindrance and orientation polarization by a zwitterionic additive to stabilize zinc metal anodes
Zinc metal stands out as a promising anode material due to its exceptional theoretical capacity, impressive energy density, and low redox potential. However, challenges such as zinc dendrite growth, anode corrosion, and side reactions in aqueous electrolytes significantly impede the practical application of zinc metal anodes. Herein, 3-(1-pyridinio)-1-propanesulfonate (PPS) is introduced as a zwitterionic additive to achieve long-term and highly reversible Zn plating/stripping. Due to the orientation polarization with the force of electric field, PPS additive with π–π conjugated pyridinio cations and strong coordination ability of sulfonate anion tends to generate a dynamic adsorption layer and build a unique water–poor interface. PPS with steric hindrance effect and strong coordination ability can attract solvated Zn2+, thereby promoting the desolvation process. Moreover, by providing a large number of nucleation sites and inducing zinc ion flow, the preferred orientation of the (002) crystal plane can be achieved. Therefore, the interfacial electrochemical reduction kinetics is regulated and uniform zinc deposition is ensured. Owing to these advantages, the Zn//Zn symmetrical cell with PPS additive exhibits remarkable cycling stability exceeding 2340 h (1 mA cm−2 and 1 mA h cm−2). The Zn//V2O5 full cell also delivers stable cycling for up to 6000 cycles.