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First-principles study on the Jahn-Teller distortion in trigonal bipyramidal coordinated LiFe1−xMxBO3 (M = Mn, Co, and Ni) compounds

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Abstract

The development of new cathode materials with high capacity, good stability, and high safety is important for the future improvement of Li batteries. LiFeBO3 is considered to be a type of promising electrode materials for Li-ion batteries due to its low cost, high theoretical capacity of 220 mAh/g (about 30% larger than that of LiFePO4), low toxicity, and small volume change of 2% during the Li+ reversible extraction/insertion process. However, its electronic conductivity and rate performance still need further improvement. To optimize the performance of the LiFeBO3, Mn, Cr, and Ni doping at Fe site have been studied experimentally, while the effect of minor addition of 3d transition metals on the electronic structure of LiFeBO3 is rarely investigated. Thus, density functional theory calculations corrected by on-site Coulomb interactions have been conducted to study the crystal structure and electronic property of the LiFe1−xMxBO3 (M = Mn, Co, and Ni) electrode systems. The results indicate that the coordination geometry about Fe in LiFeBO3 is a distorted trigonal bipyramid with a distortion which can be attributed to a Jahn-Teller effect. The band gap energy of LiFeBO3 is calculated to be 3.40 eV, which is in reasonable agreement with the previously computed values. The doping at Fe site with Mn cannot reduce the distortion of Jahn-Teller effect, whereas Co doping intensifies Jahn-Teller distortion of the FeO5 trigonal bipyramid in LiFeBO3. Ni substitution is predicted to be able to introduce impurity levels, and the Jahn-Teller distortion degree of the trigonal bipyramid decreased from 11.9 of the FeO5 to 8.7% of the NiO5. Thus, Ni doping is expected to increase stability and the electronic conductivity of the LiFeBO3 structure.

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  • 13 November 2020

    A Correction to this paper has been published: <ExternalRef><RefSource>https://doi.org/10.1007/s10008-020-04869-8</RefSource><RefTarget Address="10.1007/s10008-020-04869-8" TargetType="DOI"/></ExternalRef>

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Funding

This work was supported by the Open Research Subject of Powder Metallurgy Engineering Technology Research Center of Sichuan Province, China (grant nos. SC-FMYJ2017-03, SC-FMYJ2018-02).

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Author notes

  1. Fayou Jiang and Shanhua Chen contributed equally to this work.

Authors and Affiliations

  1. College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu, 610059, China

    Fayou Jiang, Shanhua Chen, Haonan Zhang, Endong Liu, Taishan Li, Lin Deng & Xiaodong Zhu

  2. College of Mechanical Engineering, Chengdu University, Chengdu, 610106, China

    Xiaolian Wang & Xiaodong Zhu

  3. School of Science, Xichang University, Xichang, 615000, China

    Yuli Di

  4. Key Laboratory of Computational Physics of Sichuan Province, Yibin University, Yibin, 644000, China

    Duohui Huang

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  1. Fayou Jiang
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  2. Shanhua Chen
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  4. Xiaolian Wang
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Correspondence to Shanhua Chen or Xiaolian Wang.

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The original online version of this article was revised: One of the author should be named as "Haonan Zhang" rather than "Haonang Zhang”

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Jiang, F., Chen, S., Zhang, H. et al. First-principles study on the Jahn-Teller distortion in trigonal bipyramidal coordinated LiFe1−xMxBO3 (M = Mn, Co, and Ni) compounds. J Solid State Electrochem 25, 627–635 (2021). https://doi.org/10.1007/s10008-020-04836-3

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