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An in situ reduction strategy toward dendrite-free Zn anodes

一种原位还原策略用于构筑无枝晶锌负极

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Abstract

Combining three-dimensional (3D) current collectors and zincophilic species is considered an efficient way to construct highly stable Zn metal anodes. Unfortunately, costly and complex preparation processes impede their practical application. Herein, a dendrite-free 3D Zn metal composite anode (Zn@ACC-600@Cu2+) has been rationally designed by plating Zn on a Cu2+-coordinated carbon cloth current collector (ACC-600@Cu2+). In particular, during the Zn nucleation process, Cu2+ is reduced in situ to metallic Cu and then forms a zincophilic Cu-Zn alloy with further Zn deposition. Density functional theory calculations and experimental observations reveal that the Cu-Zn alloy interface can not only act as a zincophilic deposition site for Zn ions but also enhance the conductivity to homogenize the electric field and Zn2+ flux. Thus, the ACC-600@Cu2+ host enables the high reversibility of Zn plating/stripping and long cycling stability for more than 410 h with a low-voltage hysteresis of 15.8 mV. As a proof-of-concept demonstration, the assembled Zn@ACC-600@Cu2+∥MnO2 full batteries show a decent rate capability and a substantially enhanced specific capacity of 110 mA h g−1 compared with the pristine carbon cloth-based full cells. This in situ reduction strategy establishes a facile method for designing 3D Zn metal composite anodes that advances the development of dendrite-free and durable Zn metal batteries.

摘要

结合了三维结构和亲锌物种的集流体构筑策略被认为是构建高稳定锌金属负极的有效方法. 然而, 高昂的成本和复杂的制备工艺阻碍了其实际应用. 本文通过在有均匀Cu{su2+}锚定的碳布集流体(ACC600@Cu{su2+})上沉积锌, 合理设计了一种稳定的三维锌金属复合阳极(Zn@ACC-600@Cu{su2+}). 在锌成核过程中, Cu{su2+}原位还原为金属Cu, 然后随着锌的进一步沉积, 碳布表面逐渐形成均匀的亲锌的Cu-Zn合金界面层. 密度泛函理论计算和实验观察表明, Cu-Zn合金界面不仅可以作为锌离子的亲锌沉积点, 而且可以提高导电率, 使电场和锌离子通量均匀化. 因此, ACC-600@Cu{su2+}集流体可以实现高的镀锌/剥离可逆性, 并在15.8 mV的极化电压下稳定循环410 h以上. 作为概念验证, 我们组装的Zn@ACC-600@Cu{su2+}∥MnO 2 全电池具有良好的电池倍率性能, 与原始碳布相比, 其比容量显著提高至110 mA h g{su−1}. 本文提出的原位还原策略为三维锌金属复合负极的设计提供了一种简便且低成本的方法, 促进了无枝晶和高稳定锌金属电池的发展.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22001236), the Program for Innovative Research Team (in Science and Technology) in Universities of Henan Province (19IRTSTHN022), and Zhengzhou University.

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Authors and Affiliations

  1. Henan Key Laboratory of Crystalline Molecular Functional Materials, Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China

    Mengqi Zhou  (周梦奇), Zhou Wu  (吴周), Rui Wang  (王锐), Guoqiang Sun  (孙国强) & Shuang-Quan Zang  (臧双全)

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  1. Mengqi Zhou  (周梦奇)
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  2. Zhou Wu  (吴周)
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  3. Rui Wang  (王锐)
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  4. Guoqiang Sun  (孙国强)
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  5. Shuang-Quan Zang  (臧双全)
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Contributions

Zhou M performed the experiments, analyzed the data and wrote the manuscript with support from Wu Z and Wang R. Sun G and Zang SQ conceived the project. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Guoqiang Sun  (孙国强) or Shuang-Quan Zang  (臧双全).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Mengqi Zhou received his BSc degree from Huanggang Normal University. He is currently a Master’s degree student at Zhengzhou University. His research interest mainly focuses on Zn anodes and current collectors of high-performance aqueous zinc-ion batteries.

Guoqiang Sun received his PhD degree from Beijing Institute of Technology. He is currently a lecturer at Zhengzhou University. His research interest focuses on the construction of anode materials for high-performance aqueous zinc-ion batteries.

Shuang-Quan Zang received his PhD degree in chemistry from Nanjing University in 2006. After postdoctoral research at The Chinese University of Hong Kong, he joined the College of Chemistry, Zhengzhou University. He is serving as the dean of the College of Chemistry and Green Catalysis Center, Zhengzhou University. His current scientific interests focus on atomically precise metal clusters, cluster-assembled materials, and functional metal-organic frameworks.

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Zhou, M., Wu, Z., Wang, R. et al. An in situ reduction strategy toward dendrite-free Zn anodes. Sci. China Mater. 66, 1757–1766 (2023). https://doi.org/10.1007/s40843-022-2308-4

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