西南石油大学Xianru He小组的一项最新研究，用位阻配位推拉二聚合物-H₂O-Zn²⁺重构长寿命锌金属水电池的溶剂化结构。相关论文发表在2024年5月4日出版的《德国应用化学》杂志上。

研究组提出了一种溶剂化界面衰减策略，该策略由一种位阻叔胺两亲性二聚电解质添加剂实现。超亲水链段与共价键合的亲脂间隔段的构型实现了位阻/配位的耦合，从而建立了H₂O-Zn²⁺-二聚体平衡的推拉动力学。这种相互作用重建了Zn²⁺的溶剂化结构，并允许形成稳定的双聚合物-无机杂化固体电解质界面(SEI)层。这种SEI层有效地屏蔽了锌金属阳极与水和阴离子的接触，显著减少了副反应。

此外，吸附在锌-金属阳极界面的二聚体调节了界面电化学还原动力学，保证了锌的均匀沉积。结果表明，含二聚体电解质的Zn-Zn对称电池具有显著的循环稳定性，超过5800 h (242天)。锌-NVO电池和锌-AC混合离子超级电容器也提供长达1440小时 (60天)的稳定循环，高容量保留率超过80%。这项研究展示了促进锌基储能装置的开发和商业化的潜力。

据介绍，水性锌金属电池由于其固有的高安全性和高性价比，是一种有前景的储能装置。然而，电化学还原过程中锌离子的不均匀沉积和阳极界面副反应，都严重阻碍了其开发和应用。

附：英文原文

Title: Reconstructing Solvation Structure by Steric Hindrance-Coordination Push-Pull of Dipolymer-H2O-Zn2+ toward Long-life Aqueous Zinc-Metal Batteries

Author: Die Luo, Xinyu Ma, Pan Du, Zuo Chen, Qiurui Lin, Yuhan Liu, Ben Niu, Xianru He, Xin Wang

Issue&Volume: 2024-05-04

Abstract: Aqueous zinc-metal batteries are prospective energy storge devices due to their intrinsically high safety and cost effectiveness. Yet, uneven deposition of zinc ions in electrochemical reduction and side reactions at the anode interface significantly hinder their development and application. Here, we propose a solvation-interface attenuation strategy enabled by a frustrated tertiary amine amphiphilic dipolymer electrolyte additive. The configuration of superhydrophilic segments with covalently bonded lipophilic spacers enables coupled steric hindrance/coordination, which establishes a balanced push-pull dynamic of dipolymer-H2O-Zn2+. Such interplay reconstructs the solvation structure of Zn2+ and allows the formation of a stable dipolymer-inorganic hybrid solid electrolyte interface (SEI) layer. This SEI layer effectively shields the zinc-metal anode from water and anions, significantly reducing side reactions. In addition, the dipolymer adsorbed at the zinc-metal anode interface regulates the interfacial electrochemical reduction kinetics and ensures uniform zinc deposition. As a result, the Zn-Zn symmetric cells with dipolymer-containing electrolyte exhibit remarkable cycling stability exceeding 5800 h (242 days). The Zn-NVO batteries and Zn-AC hybrid ion supercapacitors also deliver stable cycling for up to 1440 h (60 days) with high-capacity retention over 80%. This research demonstrates the potential to facilitate the development and commercialization of zinc-based energy storage devices.

DOI: 10.1002/anie.202401163

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202401163