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Hybrid high-performance aqueous batteries with potassium-based cathode||zinc metal anode

混合体系: 一种改善水系钾离子全电池能量密度和稳定性的有效方式

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Abstract

Aqueous potassium-based batteries (APBs) have been widely studied for their high safety and environmentally friendly properties. However, given the limitation of the electrode material and working mechanism, the APBs need further improvement in terms of the rate performance and energy density to meet the development requirements. To address the above issues, we successfully designed and assembled APBs, for the first time using Zn metal as the anode, K1.92Cu0.62Mn0.38[Fe(CN)6]0.968·□0.032·0.35H2O as the cathode, and 2 mol L−1 Zn(SO3CF3)2 + 12 mol L−1 KSO3CF3 as the electrolyte. This hybrid-ion-battery (HIB) design offers benefits including the following: (i) improvement of the working potential of APBs by selecting Zn metal as the anode, (ii) shortened ion transport path due to the dual-cation storage mechanism, and (iii) inhibition of the growth of zinc dendrite through the electrostatic shielding effect enabled by K+, which originated from the dual-cation electrolyte. As a result, the as-assembled full battery had a high working potential of 1.75 V and excellent rate performance (83.3% of original capacity was maintained at the current density of 10,000 mA g−1). Furthermore, the in-situ electrostatic shielding effect, which can significantly inhibit the dendrite growth of the Zn anode and improve the stability of the full battery, was fully revealed by theoretical phase-field simulation and comprehensive characterizations. The fascinating structure design of HIBs sheds light on the development of high-performance APBs.

摘要

水系钾基电池(APBs)因具有高安全性和环境友好的性质而被广泛研究. 然而, 由于电极材料和工作机制的限制, APBs在倍率性能和能量密度方面需要进一步提高, 以满足发展需求. 针对上述问题, 我们首次成功设计并组装了以Zn金属作为阳极, K1.92Cu0.62Mn0.38−[Fe(CN)6]0.968·□0.032·H2O0.35作为阴极, 2 mol L−1 Zn(SO3CF3)2 + 12 mol L−1 KSO3CF3作为电解液的水系钾基电池. 这种混合离子体系的设计优点是: (i) 选择金属锌作为阳极, 提高了APBs的工作电位; (ii) 双阳离子储存机制缩短了离子传输路径; (iii) 来自双阳离子电解质的K+通过静电屏蔽作用抑制了锌枝晶的生长. 因此, 组装后的全电池具有1.75 V的高工作电位, 并具有优异的倍率性能(在10,000 mA g−1的电流密度下, 保持原有容量的83.3%). 此外, 通过理论相场模拟和综合表征充分揭示了原位静电屏蔽效应, 显著抑制了锌阳极的枝晶生长, 提高了全电池稳定性. 混合离子电池的结构设计为高性能APBs的发展提供了思路.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (U20A20247 and 51922038).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Physics and Electronics, Hunan University, Changsha, 410082, China

    Weijian Yu  (于伟健), Junmin Ge  (盖军民), Yanyao Hu  (胡艳瑶), Dongyang Shen  (沈东阳), Wendi Luo  (罗文迪), Lichen Wu  (武利琛), Hongguan Yang  (杨红官) & Bingan Lu  (鲁兵安)

  2. School of Physics and Electronics, Henan University, Kaifeng, 475004, China

    Suhua Chen  (陈素华)

  3. School of Metallurgy, Northeastern University, Shenyang, 110819, China

    Zhaomeng Liu  (刘朝孟)

  4. School of Materials Science and Engineering, Key Laboratory of Electronic Packaging and Advanced Functional Materials of Hunan province, Central South University, Changsha, 410083, China

    Jiang Zhou  (周江)

  5. State Key Laboratory of Advanced and Manufacturing for Vehicle Body, Hunan University, Changsha, 410082, China

    Bingan Lu  (鲁兵安)

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  1. Weijian Yu  (于伟健)
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Contributions

Author contributions Yu W and Ge J conducted the experiment; Wu L and Luo W did some characterizations. Lu B, Hu Y, Shen D and Chen S performed some data analysis and offered helpful suggestions. Liu Z, Zhou J and Yang H designed this study. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Hongguan Yang  (杨红官) or Bingan Lu  (鲁兵安).

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Conflict of interest The authors declare that they have no conflict of interest.

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Supplementary information Supporting data are available in the online version of the paper.

Weijian Yu received his BSc and master degrees in electronic science and technology from Hunan University (HNU) in 2019. He is currently a doctoral candidate at Harbin Institute of Technology (HIT). His research interests focus on the modification of electrolytes for Li/Na/Zn-ion batteries.

Junmin Ge received his doctorate degree from the Department of Physics and Electronics, HNU in 2021. He is currently a researcher at Zhengzhou University. His research interests focus on noval high-safety energy storage batteries.

Bingan Lu is a professor and doctoral supervisor at HNU. Prof. Lu’s research mainly focuses on the research of new energy storage materials and devices including Li/K/Al-ion batteries. He is on the Editorial Board or Youth Editorial Board of National Science Review, Molecules, Science China Technological Sciences, InfoMat, and SmartMat.

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Yu, W., Ge, J., Hu, Y. et al. Hybrid high-performance aqueous batteries with potassium-based cathode||zinc metal anode. Sci. China Mater. 66, 923–931 (2023). https://doi.org/10.1007/s40843-022-2213-y

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  • DOI: https://doi.org/10.1007/s40843-022-2213-y

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