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通过原位监测和改进电池验证的带有多个酰胺基团的支链分子用于加速锌负极

Branched Molecule Carrying Multiple Amide Groups for Accelerating Zinc Anode, Testified by In Situ Monitoring and Improved Batteries.

作者信息

Chen Yufeng, Yang Lu, Peng Yuxin, Yi Xue, Yi Xianli, Li Hongru, Wang Zhiyong, Gao Fang

机构信息

College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China.

出版信息

Langmuir. 2025 Aug 19;41(32):21684-21696. doi: 10.1021/acs.langmuir.5c02667. Epub 2025 Aug 5.

Abstract

Rechargeable aqueous zinc-ion batteries (ZIBs) have been recognized as a promising next generation of second-level energy storage systems, with fine characteristics of pronounced low cost and safety. However, zinc dendrite growth, zinc corrosion, and side reactions on the Zn anode surface in aqueous electrolyte cause severe challenges for the practical application of aqueous ZIBs. Inspired by protein facial film, this study proposed to employ low concentrations (10 mol/L magnitude, 5.16 × 10 wt %) of an amphilic, zincophilic, and ecofriendly branched molecule based on an ethylenediamine core, showing strong intra/inter modular hydrogen bonding, as an additive in zinc sulfate electrolyte to stabilize the zinc anode and improve aqueous zinc-ion cells. A variety of in situ and ex-situ surface and electrochemical means were used to uncover increased aqueous ZIBs by the studied additive in the electrolyte. It is demonstrated that this additive was firmly adsorbed on the zinc anode surface to inhibit the growth of zinc dendrite, corrosion, and side reactions in aqueous ZIBs by tuning zinc ion deposition kinetics and the desolvation of zinc ions in water-based electrolyte solution; thus, aqueous zinc-ion cells were greatly improved. For instance, symmetric Zn||Zn batteries including 5 × 10 mol/L of the surveyed additive in the electrolyte showed long cycle stability of over 2700 h under 1mA·cm, 1 mAh·cm at 298 K, 750 h at 45 °C, and 480 h at 55 °C. The full Zn||MnO batteries carrying the studied additive displayed higher capacity and slower decay than those containing blank ZnSO electrolyte after 2000 cycles, even at a high current density of 1 A·g. This work provides valuable insights into the realization of rechargeable aqueous zinc-ion cells using a dendritic molecular additive including multiple amide groups in the electrolyte.

摘要

可充电水系锌离子电池(ZIBs)被认为是下一代有前景的二级储能系统,具有显著的低成本和安全性等优良特性。然而,水系电解质中锌枝晶生长、锌腐蚀以及锌阳极表面的副反应给水系ZIBs的实际应用带来了严峻挑战。受蛋白质面膜的启发,本研究提出在硫酸锌电解质中加入低浓度(10 mol/L量级,5.16×10 wt%)的一种基于乙二胺核心的两亲、亲锌且环保的支化分子,该分子表现出强的分子内/分子间氢键,以此来稳定锌阳极并改善水系锌离子电池。使用了多种原位和非原位表面及电化学手段来揭示电解质中所研究的添加剂对水系ZIBs性能的提升。结果表明,该添加剂通过调节锌离子沉积动力学和锌离子在水基电解质溶液中的去溶剂化作用,牢固地吸附在锌阳极表面,从而抑制水系ZIBs中锌枝晶的生长、腐蚀和副反应;因此,水系锌离子电池得到了极大改善。例如,在电解质中含有5×10 mol/L所研究添加剂的对称Zn||Zn电池在298 K下1 mA·cm²、1 mAh·cm²的电流密度下显示出超过2700 h的长循环稳定性,在45℃下为750 h,在55℃下为480 h。携带所研究添加剂的全Zn||MnO₂电池在2000次循环后,即使在1 A·g⁻¹的高电流密度下,也比含有空白ZnSO₄电解质的电池表现出更高的容量和更慢的衰减。这项工作为在电解质中使用包含多个酰胺基团的树枝状分子添加剂来实现可充电水系锌离子电池提供了有价值的见解。

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