水系锌金属二次电池中稳固的ZnS界面相研究

熊凌云; 付豪; 韩伟伟; 王慢想; 李京伟; Woochul Yang; 刘桂成

doi:10.1007/s12613-022-2454-z

Volume 29 Issue 5

Apr. 2022

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文章导航 > 矿物冶金与材料学报（英文） > 2022 > 29(5): 1053-1060

Lingyun Xiong, Hao Fu, Weiwei Han, Manxiang Wang, Jingwei Li, Woochul Yang, and Guicheng Liu, Robust ZnS interphase for stable Zn metal anode of high-performance aqueous secondary batteries, Int. J. Miner. Metall. Mater., 29(2022), No. 5, pp. 1053-1060. https://doi.org/10.1007/s12613-022-2454-z

Cite this article as:

Lingyun Xiong, Hao Fu, Weiwei Han, Manxiang Wang, Jingwei Li, Woochul Yang, and Guicheng Liu, Robust ZnS interphase for stable Zn metal anode of high-performance aqueous secondary batteries, Int. J. Miner. Metall. Mater., 29(2022), No. 5, pp. 1053-1060. https://doi.org/10.1007/s12613-022-2454-z

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研究论文

水系锌金属二次电池中稳固的ZnS界面相研究

1)
东国大学物理学院, 首尔04620, 韩国
2)
合肥工业大学材料与工程学院, 合肥230009, 中国
3)
延安大学物理与电子信息学院, 陕西延安716000, 中国

通讯作者:
Woochul Yang E-mail: wyang@dongguk.edu

刘桂成 E-mail: log67@163.com

文章亮点

(1) 在锌金属表面构建稳定的ZnS界面层并研究其保护机理。

(2) 采用低温的液相氧化和气相硫化的方法制备厚度可控的ZnS界面层。

(3) 优化不同厚度的ZnS界面层对锌金属电极电化学性能的影响。

中文摘要

水系锌金属电池因其具有较高的理论容量、较低的成本和较好的安全性等优点，目前被认为是最有前景的水系二次电池之一。但锌金属在充放电过程中遭受到严重的析氢反应、自腐蚀和枝晶生长等缺点，会严重降低电池使用寿命和充放电效率。本文旨在通过低温液相氧化和低温气相硫化的方法在锌金属表面构筑ZnS钝化层，并在合成过程中通过控制氧化时间进一步合成ZnS厚度可控的Zn@ZnS电极。与传统高温气相合成相比（温度＞350°C），本文采用低温（160°C）温和的合成方法不仅能实现ZnS厚度可控，并且还能有效避免高温下锌金属的老化。其次，得益于ZnS钝化层的化学稳定性，所制备的Zn@ZnS电极化学稳定性得到明显提升，表现出良好的防腐性能和抑制析氢反应性能。同时，ZnS层中的Zn–S键存在电荷分布不平衡现象，在电镀和剥离过程中能够诱导锌金属均匀生长，从而抑制循环过程中枝晶的生成，进而大大提高电极使用寿命。再此，我们对ZnS厚度进行优化，发现厚度为0.75 μm 的Zn@ZnS-2电极表现出最优的诱导锌金属沉积性能，并具有最佳的综合电化学性能。最后，Zn@ZnS对称电池在0.5 mA⋅cm⁻²的电流密度下可循环300次，相应过电位为42 mV。Zn@ZnS//Ti半电池在5 mA⋅cm⁻²的电流密度下可循环200次，相应的过电位为78 mV。在Zn|| NH₄V₄O₁₀全电池中展现出优异的倍率性能。

关键词:

Research Article

Robust ZnS interphase for stable Zn metal anode of high-performance aqueous secondary batteries

+ Author Affiliations

Abstract

Abstract

Although Zn metal is an ideal anode candidate for aqueous batteries owing to its high theoretical capacity, lower cost, and safety, its service life and efficiency are damaged by severe hydrogen evolution reaction, self-corrosion, and dendrite growth. Herein, a thickness-controlled ZnS passivation layer was fabricated on the Zn metal surface to obtain Zn@ZnS electrode through oxidation–orientation sulfuration by the liquid- and vapor-phase hydrothermal processes. Benefiting from the chemical inertness of the ZnS interphase, the as-prepared Zn@ZnS electrode presents an excellent anti-corrosion and undesirable hydrogen evolution reaction. Meanwhile, the thickness-optimized ZnS layer with an unbalanced charge distribution represses dendrite growth by guiding Zn plating/stripping, leading to long service life. Consequently, the Zn@ZnS presented 300 cycles in the symmetric cells with a 42 mV overpotential, 200 cycles in half cells with a 78 mV overpotential, and superb rate performance in Zn||NH₄V₄O₁₀ full cells.
- Zn metal anode;
- dendrite-free;
- ZnS passivation layer;
- controllable thickness;
- chemical inertness;
- unbalanced charge distribution

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References

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水系锌金属二次电池中稳固的ZnS界面相研究

文章亮点

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Robust ZnS interphase for stable Zn metal anode of high-performance aqueous secondary batteries

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