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Bismuth-based metal-organic frameworks derived rod-like nanoreactors for neutral aqueous battery-type anode

铋基有机金属框架衍生的棒状纳米反应器用于中性水系电池型负极

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Abstract

Bismuth oxide (Bi2O3) has received great attention as the promising battery-type anode due to its high theoretical capacity and wide operating voltage window, yet its slow reaction kinetics and poor cyclability are major obstacles affecting the performance of energy storage devices. Herein, by employing the bismuth-based metal-organic framework (MOF) CAU-17 as both the template and precursor, the Bi-Bi2O3 nanoparticles encapsulated in carbon nanorods (Bi-Bi2O3@CNR) are fabricated through pyrolysis combining deliberate oxidation-state modulation. The Bi-Bi2O3@CNR anode exhibits enhanced electrical conductivity, fast reaction kinetics, high specific capacity, and extended lifespan in sodium sulfate electrolyte. The robust, in situ derived carbon matrix as a rod-like nanoreactor and the introduction of metallic bismuth into the bismuth oxide crystalline structure enable the Bi-Bi2O3@CNR electrode to deliver a package of optimal electrochemical performance, as evidenced by substantial physicochemical characterizations, kinetics analysis and density functional theory calculations. Consequently, the neutral aqueous Na-ion battery-supercapacitor hybrid device based on the Bi-Bi2O3@CNR anode and δ-MnO2 cathode can achieve high energy and power densities simultaneously with an ultra-wide potential window of 2.4 V. This work offers an opportunity to develop high-performance Bi2O3-based electrodes by designing kinetically favorable host structure with high stability and modulating oxidation states of the active component for the neutral aqueous battery-type anode.

摘要

氧化铋(Bi2O3)因其理论容量高与工作电位窗口宽而成为具有应用前景的电池型负极材料. 但是, 氧化铋缓慢的反应动力学与较差的循环寿命限制了其在实际器件中的应用. 在本文中, 我们以铋基金属有机框架(CAU-17)作为前驱体与模板, 通过热解法结合氧化态调节制备了一种封装在棒状多孔碳纳米反应器中的Bi-Bi2O3 纳米颗粒(Bi-Bi2O3 @C NR). 该电池型负极在硫酸钠溶液中表现出良好的导电性、快速的反应动力学、高的容量与长的循环寿命. 实验结果与密度泛函理论计算表明, 金属有机框架衍生的多孔碳基质与引入氧化铋晶格中的金属铋能够进一步提升氧化铋的电化学性能. 基于Bi-Bi2O3 @C NR 负极和δ-MnO2 正极的中性水系钠离子电池电容混合器件可以同时实现高能量和高功率密度, 同时具有2.4 V的超宽电位窗口. 本文通过设计高稳定性和反应动力学有利的主体结构及调节活性成分的氧化态, 为开发可用于中性水系电池型负极的高性能氧化铋基电极提供了新的策略.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (22072107 and 21872105), the Science & Technology Commission of Shanghai Municipality (19DZ2271500), and the Fundamental Research Funds for the Central Universities.

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Authors and Affiliations

  1. Shanghai Key Lab of Chemical Assessment and Sustainability, School of Chemical Science and Engineering, Tongji University, Shanghai, 200092, China

    Mingze Xu  (徐铭泽), Shuaiqi Gong  (巩帅奇), Yanli Niu  (牛艳丽), Kaiyan Zhang  (张开颜), Tao Liu  (刘韬) & Zuofeng Chen  (陈作锋)

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  1. Mingze Xu  (徐铭泽)
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  2. Shuaiqi Gong  (巩帅奇)
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  3. Yanli Niu  (牛艳丽)
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  4. Kaiyan Zhang  (张开颜)
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  5. Tao Liu  (刘韬)
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  6. Zuofeng Chen  (陈作锋)
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Contributions

Xu M designed this study, conducted the experiments, performed data analysis and wrote the paper; Gong S, Niu Y and Zhang K conducted some experiments; Liu T performed data analysis and revised the paper; Chen Z designed this study, performed data analysis and revised the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Tao Liu  (刘韬) or Zuofeng Chen  (陈作锋).

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Conflict of interest

The authors declare that they have no conflict of interest.

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

Mingze Xu got his bachelor degree at Lanzhou University of Technology in 2019. He is now studying for his master’s degree at Tongji University. His research interest focuses on the preparation and modification of electrode materials for aqueous zinc-ion batteries and battery-supercapacitor hybrid devices.

Tao Liu received his PhD degree and worked as a postdoctoral researcher at the University of Cambridge. He was elected to a Schlumberger Research Fellowship, Darwin College, Cambridge, in 2016 and appointed to a professorship of chemistry at Tongji University, Shanghai, in 2018. His current research interests include electrocatalysis and batteries and the development of in situ spectroscopy/spectrometry techniques to study energy conversion and storage devices.

Zuofeng Chen got his PhD degree at the University of Hong Kong in 2009 and was a postdoctoral fellow at the University of North Carolina at Chapel Hill and Duke University. He has been a full professor at the School of Chemical Science and Engineering of Tongji University since 2014. His research interest focuses on new energy materials and the electrocatalysis in energy conversion and storage systems.

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Xu, M., Gong, S., Niu, Y. et al. Bismuth-based metal-organic frameworks derived rod-like nanoreactors for neutral aqueous battery-type anode. Sci. China Mater. 66, 106–117 (2023). https://doi.org/10.1007/s40843-022-2117-x

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