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通过形成富阴离子吸附层,利用有机-水混合电解质中的痕量碘离子提高锌阳极利用率。

Boosting Zn Anode Utilization by Trace Iodine Ions in Organic-Water Hybrid Electrolytes through Formation of Anion-rich Adsorbing Layers.

作者信息

Zhou Kang, Li Zhi, Qiu Xuan, Yu Zhuo, Wang Yonggang

机构信息

Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Institute of New Energy, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Fudan University, Shanghai, 200433, China.

Department of Chemistry and the Waterloo Institute for Nanotechnology, University of Waterloo, Waterloo, N2L 3G1, Ontario, Canada.

出版信息

Angew Chem Int Ed Engl. 2023 Sep 25;62(39):e202309594. doi: 10.1002/anie.202309594. Epub 2023 Aug 21.

Abstract

Aqueous Zn batteries are attracting extensive attentions, but their application is still hindered by H O-induced Zn-corrosion and hydrogen evolution reactions. Addition of organic solvents into aqueous electrolytes to limit the H O activity is a promising solution, but at the cost of greatly reduced Zn anode kinetics. Here we propose a simple strategy for this challenge by adding 50 mM iodine ions into an organic-water (1,2-dimethoxyethane (DME)+water) hybrid electrolyte, which enables the electrolyte simultaneously owns the advantages of low H O activity and accelerated Zn kinetics. We demonstrate that the DME breaks the H O hydrogen-bond network and exclude H O from Zn solvation shell. And the I is firmly adsorbed on the Zn anode, reducing the Zn de-solvation barrier from 74.33 kJ mol to 32.26 kJ mol and inducing homogeneous nucleation behavior. With such electrolyte, the Zn//Zn symmetric cell exhibits a record high cycling lifetime (14.5 months) and achieves high Zn anode utilization (75.5 %). In particular, the Zn//VS @SS full cell with the optimized electrolyte stably cycles for 170 cycles at a low N : P ratio (3.64). Even with the cathode mass-loading of 16.7 mg cm , the full cell maintains the areal capacity of 0.96 mAh cm after 1600 cycles.

摘要

水系锌电池正吸引着广泛关注,但其应用仍受限于水诱导的锌腐蚀和析氢反应。向水系电解质中添加有机溶剂以限制水的活性是一种很有前景的解决方案,但代价是锌阳极动力学大幅降低。在此,我们针对这一挑战提出了一种简单策略,即在有机-水(1,2-二甲氧基乙烷(DME)+水)混合电解质中添加50 mM碘离子,这使得电解质同时具备低水活性和加速锌动力学的优点。我们证明,DME打破了水的氢键网络,并将水排除在锌溶剂化壳层之外。并且碘离子牢固地吸附在锌阳极上,将锌去溶剂化能垒从74.33 kJ·mol降至32.26 kJ·mol,并诱导均匀成核行为。使用这种电解质,锌//锌对称电池展现出创纪录的高循环寿命(14.5个月),并实现了高锌阳极利用率(75.5%)。特别地,采用优化电解质的锌//VS@SS全电池在低氮磷比(3.64)下稳定循环170次。即使阴极质量负载为16.7 mg·cm,全电池在1600次循环后仍保持0.96 mAh·cm的面积容量。

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