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Designing a durable high-rate K0.45Ni0.1Fe0.1Mn0.8O2 cathode for K-ion batteries: A joint study of theory and experiment

设计钾离子电池耐用高倍率K0.45Ni0.1Fe0.1Mn0.8O2正极: 理论和实验联合研究

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Abstract

K-ion batteries (KIBs) hold great promise for large-scale energy storage. However, the absence of suitable cathode materials limits their practical application. Meanwhile, rationally designing advanced cathode materials for KIBs remains an open question. In this work, based on density functional theory calculations, we find that the bond stability of Fe−O is higher than that of Co−O in layered transitional metal (TM) oxides. Additionally, the K-ion migration in the Fe-based layered TM oxide has a significantly lower activation energy barrier than that in the Co-based one. Based on this theoretical prediction, we successfully synthesized a low-cost K0.45Ni0.1Fe0.1Mn0.8O2 cathode, which shows excellent structural stability and superior K-storage properties, including durable cycle life and high-rate capability. Moreover, the designed K0.45Ni0.1Fe0.1Mn0.8O2 cathode possesses a great full-cell performance with a discharge capacity of ∼75 mA h g−1 and capacity retention of ∼80% after 100 cycles. The results show that Fe has better structural stability and K-ion diffusion than high-cost Co in layered oxide cathodes, and this finding provides new insights into the design of low-cost and high-performance KIB layered cathodes. This work highlights the feasibility of a theory-guided experiment in screening promising battery materials.

摘要

钾离子电池在大规模储能方面具有广阔的前景. 然而, 缺乏合适的正极材料限制了其实际应用. 此外, 为钾离子电池合理设计先进的正极材料仍然面临挑战. 本工作中, 通过密度泛函理论计算, 我们发现层状过渡金属氧化物中Fe−O键稳定性高于Co−O键. 此外, Fe基层状氧化物中的钾离子迁移具有明显低于Co基氧化物的活化能垒. 基于这一理论预测, 我们成功合成了一种低成本的K0.45Ni0.1Fe0.1Mn0.8O2正极, 该正极显示出优异的结构稳定性和储钾性能, 包括较长的循环寿命和高倍率性能. 此外, 所设计的K0.45Ni0.1Fe0.1Mn0.8O2正极具有良好的全电池性能, 放电容量约为75 mA h g−1, 100次循环后容量保持率约为80%. 在层状氧化物正极中, Fe比高成本Co具有更好的结构稳定性和钾离子扩散能力, 这一发现为低成本和高性能钾离子电池层状正极的设计提供了新的思路. 这项工作突出了以理论为指导的实验在筛选有前景的电池材料方面的可行性.

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Acknowledgements

This work was supported by the Fundamental Research Funds for the Central Universities and the Scientific Instrument Developing Project of the Chinese Academy of Sciences (ZDKYYQ20170001). The authors would like to thank Dr. Rui Gao for the analysis of the high-energy synchrotron X-ray diffraction (sXRD) and the staff of the 4B9A beamline at BSRF for sXRD testing.

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Authors and Affiliations

  1. College of Materials Science and Optoelectronic Technology, Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049, China

    Rongbin Dang  (党荣彬), Qing-Bo Yan  (闫清波), Na Li  (李娜), Kang Wu  (吴康), Xiangfeng Liu  (刘向峰), Zhongbo Hu  (胡中波) & Xiaoling Xiao  (肖小玲)

  2. Songshan Lake Materials Laboratory, Dongguan, 523808, China

    Enyue Zhao  (赵恩岳)

  3. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China

    Zhongjun Chen  (陈中军) & Zhonghua Wu  (吴忠华)

Authors
  1. Rongbin Dang  (党荣彬)
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  2. Qing-Bo Yan  (闫清波)
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  3. Enyue Zhao  (赵恩岳)
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  10. Xiaoling Xiao  (肖小玲)
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Contributions

Author contributions Dang R, Zhao E, and Xiao X conceived the ideas. Dang R conducted the DFT calculations with the help from Yan QB. Dang R synthesized and characterized the materials with the help from Li N and Wu K. Chen Z and Wu Z conducted the synchrotron XRD experiments. Dang R, Zhao E, and Xiao X wrote the initial draft. Zhao E and Xiao X supervised the whole work. Liu X and Hu Z participated in the data analysis and edited the manuscript. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Enyue Zhao  (赵恩岳) or Xiaoling Xiao  (肖小玲).

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

Additional information

Rongbin Dang received his PhD degree under the supervision of Prof. Xiaoling Xiao from the University of Chinese Academy of Sciences in 2021. He is currently working as a postdoctoral at the Institute of Physics, Chinese Academy of Sciences. His research focuses on the cathode materials for Na/K-ion batteries.

Enyue Zhao is currently an associate professor at Songshan Lake Materials Laboratory. He received his PhD degree in condensed matter physics from the Institute of Physics, Chinese Academy of Sciences (2019). Then, he worked at the University of California, San Diego as a postdoctoral fellow (2020–2021). His research mainly focuses on neutron-based characterization techniques and advanced electrode materials for rechargeable batteries.

Xiaoling Xiao is a professor at the College of Materials Science and Optoelectronics Technology, University of Chinese Academy of Sciences. She received her PhD degree from the University of Chinese Academy of Sciences in 2008 and worked as a postdoctoral fellow (2008–2010) at Tsinghua University. Her research interests include electrochemical energy storage for rechargeable batteries.

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40843_2021_1954_MOESM1_ESM.pdf

Designing a Durable High-Rate K0.45Ni0.1Fe0.1Mn0.8O2 Cathode for K-ion Batteries: A Joint Study of Theory and Experiment

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Dang, R., Yan, QB., Zhao, E. et al. Designing a durable high-rate K0.45Ni0.1Fe0.1Mn0.8O2 cathode for K-ion batteries: A joint study of theory and experiment. Sci. China Mater. 65, 1741–1750 (2022). https://doi.org/10.1007/s40843-021-1954-4

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