Large-scale synthesis of lithium- and manganese-rich materials with uniform thin-film Al2O3 coating for stable cathode cycling

大规模制备氧化铝均匀包覆的富锂锰基正极材料用于锂离子电池

Abstract

The lithium- and manganese-rich layered oxide (LMR) holds great promise as a cathode material for lithium-ion battery (LIB) applications due to its high capacity, high voltage and low cost. Unfortunately, its poor initial Coulombic efficiency (ICE) and unstable electrode/electrolyte interface with continuous growth of the solid electrolyte interphase leads to high impedance and large overpotential. These effects cause severe capacity loss and safety issues. In this work, we have developed a novel approach to fabricate a stable LMR cathode with a uniform thin layer of aluminum oxide (Al2O3) coated on the surface of the LMR particles. This synthesis approach uses the microemulsion method that is environment-friendly, cost-effective and can be easily scaled. Typically, an 8-nm layer of Al2O3 is shown to be effective in stabilizing the electrode/electrolyte interface (enhanced ICE to 82.0% and moderate impedance increase over 200 cycles). Moreover, the phase transformation from layered to spinel is inhibited (96.3% average voltage retention) and thermal stability of the structure is significantly increased (heat release reduced by 72.4%). This study opens up a new avenue to address interface issues in LIB cathodes and prompts the practical applications of high capacity and voltage materials for high energy density batteries.

摘要

因其高容量、 高电压和低成本的特点, 富锂锰基氧化物(LMR)作为锂离子电池(LIB)正极材料具有广阔的应用前景. 然而, 其较低的首次库仑效率(ICE)和不稳定的电极/电解质界面, 使电池阻抗较高和电压衰减较快, 从而导致电池出现较快的容量损失并引发安全问题. 在这项工作中, 我们通过微乳液法在LMR正极材料 表面均匀涂覆一层氧化铝(Al2O3), 以稳定其界面性质. 这种基于微乳液的包覆方法环境友好、 成本低, 并且可以大规模应用. 厚度为8 nm的Al2O3包覆层可有效稳定LMR电极/电解质界面(ICE提高至82.0%, 并在200圈循环内有效稳定电池阻抗). 此外, 对LMR界面的改性抑制了材料从层状到尖晶石的相变(200圈循环后放电中值电压保持率为96.3%), 并且提升了材料的热稳定性(热量释放减少了72.4%). 总之, 这项研究为解决锂离子电池正极材料的界面问题开辟了一条新途径.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (U1564205), the Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges under Beijing Municipality (IDHT20180508). Li T is thankful for the Northern Illinois University startup support

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Authors

Contributions

Author contributions Li J, Li T and Zhao Y conceived and developed the concept. Kang Y, Li J and Zhao Y prepared the materials Kang Y, Zhao Y, Xu H and Qian K contributed to the experiments. Zhao Y, Kang Y and Li T analyzed the data and wrote the manuscript. Zhao Y, Li J, He X and Liang Z reviewed and edited the manuscript before submission. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Yun Zhao 赵云 or Tao Li 李涛 or Jiangang Li 李建刚.

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

Additional information

Jiangang Li received his BSc degree in chemistry from Shanxi University in 1987. He completed his PhD in the Department of Applied Chemistry at Tianjin University in 2001. Then he carried out his postdoctoral research with Prof. Chunrong Wan in the Institute of Nuclear and New Energy Technology at Tsinghua University in 2002–2004. He worked as a visiting scholar with Prof. Guozhong Cao at the University of Washington in 2009–2010. He is currently a professor in the School of Chemical Engineering at Beijing Institute of Petrochemical Technology. His current research interests focus on the advanced materials for energy conversion and storage such as batteries and supercapacitors.

Tao Li earned his BSc degree in polymer material science and engineering from the East China University of Science and Technology in 2003. He completed his PhD in the Department of Chemistry and Biochemistry at the University of South Carolina—Columbia in 2009. He is currently an assistant professor in the Department of Chemistry and Biochemistry at Northern Illinois University and holds a joint scientist position at the Advanced Photon Source at Argonne National Lab. His research interests focus on using advanced X-ray techniques to study the self-assembly of nanoparticles as well as energy materials including catalyst and battery.

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Kang, Y., Liang, Z., Zhao, Y. et al. Large-scale synthesis of lithium- and manganese-rich materials with uniform thin-film Al2O3 coating for stable cathode cycling. Sci. China Mater. (2020). https://doi.org/10.1007/s40843-020-1327-8

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Keywords

  • lithium ion batteries
  • lithium- and manganese-rich layered oxides
  • surface modification
  • metal oxide thin film
  • uniform coating
  • large-scale synthesis
  • battery safety