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通过诱导Zn(002)生长构建高度稳定的锌金属负极

Constructing Highly Stable Zinc Metal Anodes via Induced Zn(002) Growth.

作者信息

Hu Shiyang, Tao Huachao, Ma Hui, Yan Bo, Li Yahao, Zhang Lulu, Yang Xuelin

机构信息

College of Materials and Chemical Engineering, Hubei Provincial Collaborative Innovation Center for New Energy Microgrid, China Three Gorges University, Yichang, Hubei 443002, China.

Hubei Three Gorges Laboratory, Yichang, Hubei 443007, China.

出版信息

ACS Appl Mater Interfaces. 2024 Apr 17;16(15):18949-18958. doi: 10.1021/acsami.4c01356. Epub 2024 Apr 3.

Abstract

The nonuniform electric field at the surface of a zinc (Zn) anode, coupled with water-induced parasitic reactions, exacerbates the growth of Zn dendrites, presenting a significant impediment to large-scale energy storage in aqueous Zn-ion batteries. One of the most convenient strategies for mitigating dendrite-related issues involves controlling crystal growth through electrolyte additives. Herein, we present thiamine hydrochloride (THC) as an electrolyte additive capable of effectively stabilizing the preferential deposition of the Zn(002) plane. First-principles calculations reveal that THC tends to adsorb on Zn(100) and Zn(101) planes and is capable of inducing the deposition of Zn ion onto the (002) plane and the preferential growth of the (002) plane, resulting in a flat and compact deposition layer. A THC additive not only effectively suppresses dendrite growth but also prevents the generation of side reactions and hydrogen evolution reaction. Consequently, the Zn||Zn symmetric battery exhibits long-term cycling stability of over 3000 h at 1 mA cm/1 mAh cm and 1000 h at 10 mA cm/10 mAh cm. Furthermore, the NHVO||Zn full battery also displays excellent cycling stability and a high reversible capacity of 210 mAh g after 1000 cycles at 1 A g, highlighting a significant potential for practical applications.

摘要

锌(Zn)阳极表面的非均匀电场,加上水引发的寄生反应,加剧了锌枝晶的生长,这对水系锌离子电池的大规模储能构成了重大障碍。缓解枝晶相关问题最便捷的策略之一是通过电解质添加剂来控制晶体生长。在此,我们提出将盐酸硫胺(THC)作为一种能够有效稳定Zn(002)平面优先沉积的电解质添加剂。第一性原理计算表明,THC倾向于吸附在Zn(100)和Zn(101)平面上,并能够诱导锌离子沉积到(002)平面上,以及(002)平面的优先生长,从而形成一个平整致密的沉积层。THC添加剂不仅能有效抑制枝晶生长,还能防止副反应和析氢反应的发生。因此,Zn||Zn对称电池在1 mA cm/1 mAh cm条件下表现出超过3000小时的长期循环稳定性,在10 mA cm/10 mAh cm条件下表现出1000小时的长期循环稳定性。此外,NHVO||Zn全电池在1 A g下经过1000次循环后也表现出优异的循环稳定性和210 mAh g的高可逆容量,凸显了其在实际应用中的巨大潜力。

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