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In situ construction of amorphous hierarchical iron oxyhydroxide nanotubes via selective dissolution-regrowth strategy for enhanced lithium storage

选择性溶解-再生长策略原位构筑非晶羟基氧化铁分级纳米管增强储锂性能

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Abstract

The low-cost and high-capacity metal oxides/oxyhydroxides possess great merits as anodes for lithium-ion batteries (LIBs) with high energy density. However, their commercialization is greatly hindered by insufficient rate capability and cyclability. Rational regulations of metal oxides/oxyhydroxides with hollow geometry and disordered atomic frameworks represent efficient ways to improve their electrochemical properties. Herein, we propose a fast alkalietching method to realize the in-situ fabrication of iron oxyhydroxide with one-dimensional (1D) hierarchical hollow nanostructure and amorphous atomic structure from the iron vanadate nanowires. Benefiting from the improved electron/ ion kinetics and efficient buffer ability for the volumetric change during the electro-cycles both in nanoscale and atomic level, the graphene-modified amorphous hierarchical FeOOH nanotubes (FeOOH-NTs) display high rate capability (~650 mA h g−1 at 2000 mA g−1) and superior long-term cycling stability (463 mA h g−1 after 1800 cycles), which represents the best cycling performance among the reported FeOOH-based materials. More importantly, the selective dissolutionregrowth mechanism is demonstrated based on the time tracking of the whole transition process, in which the dissolution of FeVO4 and the in-situ selective re-nucleation of FeOOH during the formation of FeOOH-NTs play the key roles. The present strategy is also a general method to prepare various metal (such as Fe, Mn, Co, and Cu) oxides/oxyhydroxides with 1D hierarchical nanostructures.

摘要

低成本、 高容量金属氧化物/氢氧化物作为具有更高能量密度的锂离子电池的负极材料时具有显著优势. 合理调控金属氧化物/氢氧化物的中空结构和无序的原子框架是提高其电化学性能的有效途径. 本文提出了一种快速碱刻蚀方法, 实现了非晶FeOOH分级纳米管的原位构筑. 得益于增强的电子/离子动力学和对循环过程中的体积变化的有效缓冲, 石墨烯修饰的非晶FeOOH分级纳米管展现出高倍率性能(在2000 mA g−1的电流密度下容量可达~650 mA h g−1)和优异的循环稳定性(循环1800次后容量仍保持在463 mA h g−1), 在目前报道的FeOOH基材料中处于领先水平. 研究表明碱刻蚀过程中的选择性溶解-再生长机制, 即FeVO4的溶解和FeOOH的原位成核再生长在非晶FeOOH分级纳米管的合成过程中具有重要作用. 此外, 这种选择性溶解-再生长机制是一种合成具有一维分级纳米结构的金属(例如Fe, Mn, Co和Cu)氧化物/羟基氧化物的普适方法.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2017YFE0127600, 2016YFA0202600), the Program of Introducing Talents of Discipline to Universities (B17034), the National Natural Science Foundation of China (51521001 and 51602239), the National Natural Science Fund for Distinguished Young Scholars (51425204), Hubei Provincial Natural Science Foundation (2016CFB267), and the Fundamental Research Funds for the Central Universities (WUT: 2017-YB-001).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China

    Fangyu Xiong  (熊方宇), Chen Tang  (汤臣), Pengfei Zhang  (张鹏飞), Shuangshuang Tan  (谭双双), Qinyou An  (安琴友) & Liqiang Mai  (麦立强)

  2. Department of Materials Science & Engineering, College of Engineering, Peking University, Beijing, 100871, China

    Fan Lv  (吕帆) & Shaojun Guo  (郭少军)

  3. Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Foshan, 528200, China

    Qinyou An  (安琴友) & Liqiang Mai  (麦立强)

  4. BIC-ESAT, College of Engineering, Peking University, Beijing, 100871, China

    Shaojun Guo  (郭少军)

  5. Beijing Key Laboratory for Magnetoeletric Materials and Devices (BKL-MEMD), Peking University, Beijing, 100871, China

    Shaojun Guo  (郭少军)

Authors
  1. Fangyu Xiong  (熊方宇)
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  3. Chen Tang  (汤臣)
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Contributions

Author contributions Mai L, Guo S, An Q, Lv F and Xiong F conceived the study. Lv F, Tang C and Xiong F carried out the experiments. Xiong F, Lv F, Tang C, Zhang P and Tan S participated in the data analysis. Xiong F and Lv F wrote the manuscript and Mai L, Guo S and An Q provided insights for the experiments and supervised the research. Tang C, Zhang P and Tan S modified the manuscript. All authors approved the final manuscript.

Corresponding authors

Correspondence to Qinyou An  (安琴友), Shaojun Guo  (郭少军) or Liqiang Mai  (麦立强).

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Conflict of interest The authors declare no conflict of interest.

Additional information

Fangyu Xiong received his BSc degree in material physics from Wuhan University of Technology (WUT) in 2016. He is currently pursuing his PhD degree and his current research interest focuses on the electrode materials for emerging energy storage devices.

Fan Lv is currently a PhD student in the Department of Materials Science and Engineering, Peking University under the supervision of Prof. Shaojun Guo. His current research interests focus on the development of nanostructured advanced energy materials for electrocatalysis.

Qinyou An is Associate Professor of materials science and engineering at WUT. He received his PhD degree from WUT in 2014. He carried out his postdoctoral research in the Laboratory of Prof. Yan Yao at the University of Houston in 2014–2015. Currently, his research interest includes energy storage materials and devices.

Liqiang Mai is the Chair Professor of materials science and engineering at WUT. He received his PhD from WUT in 2004. He carried out his postdoctoral research in the Laboratory of Prof. Zhonglin Wang at Georgia Institute of Technology in 2006–2007 and worked as an advanced research scholar in the Laboratory of Prof. Charles M. Lieber at Harvard University in 2008–2011. His current research interests focus on nanowire materials and devices for energy storage.

Shaojun Guo received his BSc degree from Jilin University (2005) and PhD degree from the Chinese Academy of Sciences (2010). He worked as a postdoctoral researcher associate at Brown University (2011–2013) and as a prestigious Oppenheimer Distinguished Fellow at Los Alamos National Laboratory (2013–2015). He joined the College of Engineering, Peking University in 2015 and is currently a Professor. His research interests focus on engineering nanocrystals and 2D materials for catalysis, renewable energy, optoelectronics and biosensors.

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40843_2020_1337_MOESM1_ESM.pdf

In situ construction of amorphous hierarchical iron oxyhydroxide nanotubes via selective dissolution-regrowth strategy for enhanced lithium storage

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Xiong, F., Lv, F., Tang, C. et al. In situ construction of amorphous hierarchical iron oxyhydroxide nanotubes via selective dissolution-regrowth strategy for enhanced lithium storage. Sci. China Mater. 63, 1993–2001 (2020). https://doi.org/10.1007/s40843-020-1337-5

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