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Engineering oxygen vacancies in hierarchically Li-rich layered oxide porous microspheres for high-rate lithium ion battery cathode

氧空位提升锂离子电池富锂锰基正极分级多孔微米球的高倍率性能

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Abstract

Lithium-rich layered oxides always suffer from low initial Coulombic efficiency, poor rate capability and rapid voltage fading. Herein, engineering oxygen vacancies in hierarchically Li1.2Mn0.54Ni0.13Co0.13O2 porous microspheres (L@S) is carried out to suppress the formation of irreversible Li2O during the initial discharge process and improve the Li+ diffusion kinetics and structural stability of the cathode mateiral. As a result, the prepared L@S cathode delivers high initial Coulombic efficiency of 92.3% and large specific capacity of 292.6 mA h g−1 at 0.1 C. More importantly, a large reversible capacity of 222 mA h g−1 with a capacity retention of 95.7% can be obtained after 100 cycles at 10 C. Even cycled at ultrahigh rate of 20 C, the L@S cathode can deliver stable reversible capacity of 153 mA h g−1 after 100 cycles. Moreover, the full cell using L@S as cathode and Li4Ti5O12 as anode exhibits a relatively high reversible capacity of 141 mA h g−1 with an outstanding voltage retention of 97% after 400 cycles at a large current density of 3 C. These results may shed light on the improvement of electrochemical performances of lithium-rich layered oxides via the multiscale coordinated design based on atomic defects, microstructure and composition.

摘要

富锂锰基正极材料存在首次库仑效率低、 倍率性能差以及电压衰减严重等问题, 极大地限制了其规模化应用. 本文通过在富锂锰基分级多孔微米球的表面构筑氧空位(L@S)成功抑制了首次放电过程中不可逆Li2O的形成, 有效促进了Li+离子的扩散动力学, 从而提高了电极材料的结构稳定性. 研究结果表明, L@S正极在0.1 C电流密度下循环的首次库仑效率高达92.3%, 放电比容量为292.6 mA h g−1; 在10 C大电流密度下循环100圈后可逆比容量为222 mA h g−1, 容量保持率为95.7%. 进一步增大电流密度至20 C时, 循环100圈后L@S正极的放电比容量仍高达153 mA h g−1. 此外, 匹配Li4Ti5O12负极组装的全电池在3 C电流密度下循环400圈后的可逆比容量为141 mA h g−1, 电压保持率高达97%.

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Acknowledgements

The authors acknowledge the support from the National Key R&D Program of China (2016YFA0202602 and 2016YFA0202604), the National Natural Science Foundation of China (51701169 and 51871188), the Natural Science Foundation of Fujian Province (2017J05087), the Key Projects of Youth Natural Foundation for the Universities of Fujian Province of China (JZ160397), and the “Double-First Class” Foundation of Materials and Intelligent Manufacturing Discipline of Xiamen University.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, State Key Lab of Physical Chemistry of Solid Surface, Collaborative Innovation Center of Chemistry for Energy Materials, College of Materials, Xiamen University, Xiamen, 361005, China

    Yuxin Cai  (蔡余新), Lun Ku  (库伦), Laisen Wang  (王来森), Yating Ma  (麻亚挺), Hongfei Zheng  (郑鸿飞), Wanjie Xu  (徐万杰), Jiangtao Han  (韩江涛), Yuanzhi Chen  (陈远志), Qingshui Xie  (谢清水) & Dong-Liang Peng  (彭栋梁)

  2. Pen-Tung Sah Institute of Micro-Nano Science and Technology, Xiamen University, Xiamen, 361005, China

    Baihua Qu  (瞿佰华)

Authors
  1. Yuxin Cai  (蔡余新)
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  2. Lun Ku  (库伦)
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  3. Laisen Wang  (王来森)
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  4. Yating Ma  (麻亚挺)
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  5. Hongfei Zheng  (郑鸿飞)
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  6. Wanjie Xu  (徐万杰)
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  7. Jiangtao Han  (韩江涛)
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  8. Baihua Qu  (瞿佰华)
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  9. Yuanzhi Chen  (陈远志)
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  10. Qingshui Xie  (谢清水)
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  11. Dong-Liang Peng  (彭栋梁)
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Contributions

Author contributions Cai Y and Ku L designed the materials; Cai Y, Ma Y and Zheng H performed the experiments; Han J and Xu W analyzed the data; Cai Y wrote the paper with support from Wang L and Xie Q; Peng DL, Xie Q, Chen Y and Qu B contributed to the theoretical analysis. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Laisen Wang  (王来森), Qingshui Xie  (谢清水) or Dong-Liang Peng  (彭栋梁).

Additional information

Conflict of interest The authors declare no conflict of interest.

Yuxin Cai received his BE degree from the Department of Materials Science and Engineering, Shandong University. Currently, he is a ME candidate at the Department of Materials Science and Engineering in Xiamen University under the supervision of Prof. Lai-Sen Wang. His research focuses on the design and synthesis of high-performance cathode materials for lithium ion batteries.

Lai-Sen Wang is an Associated Professor in the Department of Materials Science and Engineering, College of Materials, Xiamen University. He received his PhD degree in materials physics and chemistry at Xiamen University in 2012. His research focuses on the electromagnetic transport property of thin films and the design and synthesis of nanocomposite materials for energy storage.

Qingshui Xie is an Associated Professor in the College of Materials, Xiamen University. He got his BSc and MSc degrees from Lanzhou University in 2009 and 2012, respectively. After that, he moved to Xiamen University as a PhD candidate and received his PhD degree in materials physics and chemistry in 2015. His research interest concentrates on the advanced electrode materials for high-performance lithium ion batteries.

Dong-Liang Peng received his BSc (1983), MSc (1989) and PhD (1997) degrees in condensed matter physics from Lanzhou University. He received another PhD degree in materials science and engineering from Nagoya Institute of Technology (Japan) in 2002. Currently he is a Professor in the College of Materials, Xiamen University. He received the National Natural Science Fund for Distinguished Young Scholars. His research focuses on the nano functional materials, and their applications in catalysis, energy storage and electromagnetics.

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Engineering oxygen vacancies in hierarchically porous Li-rich layered oxide microspheres for high-rate lithium ion battery cathode

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Cai, Y., Ku, L., Wang, L. et al. Engineering oxygen vacancies in hierarchically Li-rich layered oxide porous microspheres for high-rate lithium ion battery cathode. Sci. China Mater. 62, 1374–1384 (2019). https://doi.org/10.1007/s40843-019-9456-1

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