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在优先的锌(100)晶面以六边形图案操纵锌沉积行为以构建无表面枝晶的锌金属阳极。

Manipulating the Zinc Deposition Behavior in Hexagonal Patterns at the Preferential Zn (100) Crystal Plane to Construct Surficial Dendrite-Free Zinc Metal Anode.

作者信息

Zhang Yaru, Han Xinpeng, Liu Runze, Yang Zhanxu, Zhang Shaojie, Zhang Yiming, Wang Huili, Cao Yu, Chen Aibing, Sun Jie

机构信息

Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China.

College of Chemistry, Chemical Engineering and Environment Engineering, Liaoning Shihua University, Fushun, Liaoning, 113001, China.

出版信息

Small. 2022 Feb;18(7):e2105978. doi: 10.1002/smll.202105978. Epub 2021 Dec 8.

Abstract

Zinc metal has a severe dendrite issue caused by the uneven Zn plating/stripping during continual cycles, which hinders the practical application of ZIBs. The surficial atomic structure of zinc anode plays a decisive role in solving dendrites and improving the electrochemical performance. According to the density functional theory results, Zn (100) plane possesses a much stronger adsorption energy of zinc atom compared with the (002), thus zinc atom preferentially nucleates on the (100) surface. It subsequently continues to grow vertically on (100). Herein, the zinc anode is designed with hexagonal-hole patterns (h-Zn) through a phosphoric acid etching reaction. An abundance of Zn (100) crystal planes are exposed perpendicularly to the anode surface, while the (002) surfaces are at the bottom of these hexagonal holes. Zinc prefers to deposit in hexagonal holes at the (100) surfaces, favoring the restraining of the surficial dendrite growth and accelerating the Zn deposition kinetics. Thus, the symmetric cell using h-Zn exhibits a long cycling lifespan for over 1200 h and extremely low polarization voltage of ≈80 mV at 5 mA cm and 1 mAh cm . This work provides an insight into the surficial structure design and crystal plane regulation to fabricate brilliant zinc metal anodes.

摘要

锌金属存在严重的枝晶问题,这是由连续循环过程中锌镀层/剥离不均匀导致的,这阻碍了水系锌离子电池的实际应用。锌阳极的表面原子结构在解决枝晶问题和改善电化学性能方面起着决定性作用。根据密度泛函理论结果,与(002)面相比,Zn(100)面具有更强的锌原子吸附能,因此锌原子优先在(100)表面成核。随后它在(100)面上继续垂直生长。在此,通过磷酸蚀刻反应设计了具有六边形孔图案的锌阳极(h-Zn)。大量的Zn(100)晶面垂直于阳极表面暴露,而(002)面位于这些六边形孔的底部。锌更倾向于沉积在(100)面的六边形孔中,这有利于抑制表面枝晶生长并加速锌沉积动力学。因此,使用h-Zn的对称电池在5 mA cm²和1 mAh cm²时表现出超过1200 h的长循环寿命和约80 mV的极低极化电压。这项工作为制造优异的锌金属阳极的表面结构设计和晶面调控提供了思路。

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