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通过具有分子-离子转换机制的烟酸电解质添加剂实现无枝晶且无副产物的水系锌离子电池阳极

Achieving Dendrite-Free and By-Product-Free Aqueous Zn-Ion Battery Anode via Nicotinic Acid Electrolyte Additive with Molecule-Ion Conversion Mechanism.

作者信息

Liang Hanhao, Wu Jian, Li Jiaming, Wang Jianglin, Yang Zhanhong, Wu Yuping

机构信息

Hunan Province Key Laboratory of Chemical Power Source, College of Chemistry and Chemical Engineering, Central South University, Changsha, 410083, China.

Innovation Base of Energy and Chemical Materials for Graduate Students Training, Central South University, Changsha, 410083, China.

出版信息

Small. 2024 Sep;20(38):e2402595. doi: 10.1002/smll.202402595. Epub 2024 May 19.

DOI:10.1002/smll.202402595
PMID:38764288
Abstract

The widespread adoption of aqueous Zn ion batteries is hindered by the instability of the Zn anode. Herein, an elegant strategy is proposed to enhance the stability of Zn anode by incorporating nicotinic acid (NA), an additive with a unique molecule-ion conversion mechanism, to optimize the anode/electrolyte interface and the typical ZnSO electrolyte system. Experimental characterization and theoretical calculations demonstrate that the NA additive preferentially replaces HO in the original solvation shell and adsorbs onto the Zn anode surface upon conversion from molecule to ion in the electrolyte environment, thereby suppressing side reactions arising from activated HO decomposition and stochastic growth of Zn dendrites. Simultaneously, such a molecule-to-ion conversion mechanism may induce preferential deposition of Zn along the (002) plane. Benefiting from it, the Zn||Zn symmetric battery cycles stably for 2500 h at 1 mA cm, 1 mAh cm. More encouragingly, the Zn||AC full batteries and the Zn||AC full batteries using NA electrolyte and Zn||VO full batteries also exhibit excellent performance improvements. This work emphasizes the role of variation in the form of additives (especially weak acid-based additives) in fine-tuning the solvation structure and the anode/electrolyte interface, hopefully enhancing the performance of various aqueous metal batteries.

摘要

锌阳极的不稳定性阻碍了水系锌离子电池的广泛应用。在此,我们提出了一种巧妙的策略,通过引入烟酸(NA)来提高锌阳极的稳定性。烟酸是一种具有独特分子-离子转换机制的添加剂,用于优化阳极/电解质界面以及典型的ZnSO电解质体系。实验表征和理论计算表明,在电解质环境中,NA添加剂优先取代原始溶剂化壳层中的HO,并在从分子转化为离子后吸附在锌阳极表面,从而抑制由活化的HO分解和锌枝晶的随机生长引起的副反应。同时,这种分子到离子的转换机制可能会诱导锌沿(002)平面优先沉积。受益于此,Zn||Zn对称电池在1 mA cm、1 mAh cm的条件下稳定循环2500小时。更令人鼓舞的是,使用NA电解质的Zn||AC全电池以及Zn||AC全电池和Zn||VO全电池也表现出优异的性能提升。这项工作强调了添加剂形式变化(特别是基于弱酸的添加剂)在微调溶剂化结构和阳极/电解质界面方面的作用,有望提高各种水系金属电池的性能。

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