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非共价相互作用驱动的聚阴离子添加剂自组装用于长效抗日历老化和高倍率锌金属电池

Noncovalent Interactions-Driven Self-Assembly of Polyanionic Additive for Long Anti-Calendar Aging and High-Rate Zinc Metal Batteries.

作者信息

Yang Zimin, Sun Yilun, Li Jianwei, He Guanjie, Chai Guoliang

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, P. R. China.

College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, Fujian, 350007, P. R. China.

出版信息

Adv Sci (Weinh). 2024 Sep;11(33):e2404513. doi: 10.1002/advs.202404513. Epub 2024 Jun 27.

Abstract

Zinc anodes of zinc metal batteries suffer from unsatisfactory plating/striping reversibility due to interfacial parasitic reactions and poor Zn mass transfer kinetics. Herein, methoxy polyethylene glycol-phosphate (mPEG-P) is introduced as an electrolyte additive to achieve long anti-calendar aging and high-rate capabilities. The polyanionic of mPEG-P self-assembles via noncovalent-interactions on electrode surface to form polyether-based cation channels and in situ organic-inorganic hybrid solid electrolyte interface layer, which ensure rapid Zn mass transfer and suppresses interfacial parasitic reactions, realizing outstanding cycling/calendar aging stability. As a result, the Zn//Zn symmetric cells with mPEG-P present long lifespans over 9000 and 2500 cycles at ultrahigh current densities of 120 and 200 mA cm, respectively. Besides, the coulombic efficiency (CE) of the Zn//Cu cell with mPEG-P additive (88.21%) is much higher than that of the cell (36.4%) at the initial cycle after the 15-day calendar aging treatment, presenting excellent anti-static corrosion performance. Furthermore, after 20-day aging, the Zn//MnO cell exhibits a superior capacity retention of 89% compared with that of the cell without mPEG-P (28%) after 150 cycles. This study provides a promising avenue for boosting the development of high efficiency and durable metallic zinc based stationary energy storage system.

摘要

锌金属电池的锌阳极由于界面寄生反应和较差的锌传质动力学,其电镀/脱镀可逆性不尽人意。在此,引入甲氧基聚乙二醇磷酸酯(mPEG-P)作为电解质添加剂,以实现长循环寿命和高倍率性能。mPEG-P的聚阴离子通过非共价相互作用在电极表面自组装,形成基于聚醚的阳离子通道和原位有机-无机混合固体电解质界面层,确保了快速的锌传质并抑制了界面寄生反应,实现了出色的循环/日历老化稳定性。结果,含有mPEG-P的Zn//Zn对称电池在120和200 mA cm的超高电流密度下分别具有超过9000次和2500次的长循环寿命。此外,经过15天的日历老化处理后,含有mPEG-P添加剂的Zn//Cu电池在初始循环时的库仑效率(CE)(88.21%)远高于不含该添加剂的电池(36.4%),表现出优异的抗静电腐蚀性能。此外,经过20天老化后,Zn//MnO电池在150次循环后表现出89%的优异容量保持率,相比之下,不含mPEG-P的电池在150次循环后的容量保持率为28%。这项研究为推动高效耐用的金属锌基固定储能系统的发展提供了一条有前景的途径。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2937/11434035/98ab735414f1/ADVS-11-2404513-g008.jpg

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