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Identifying the intrinsic anti-site defect in manganese-rich NASICON-type cathodes

Nature Energy volume 8, pages 1088–1096 (2023)Cite this article

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Abstract

Manganese-rich NASICON-type materials have triggered widespread attention for developing advanced polyanionic cathodes, primarily driven by their abundant reserves and promising cycling performance with high operating voltages (~3.8 V for Mn2+/3+/4+, versus Na+/Na). However, the charge/discharge profiles exhibit significant voltage hysteresis, which leads to a limited reversible capacity, thereby preventing their application. Here, we demonstrate that the voltage hysteresis in manganese-rich NASICON-type cathodes (Na3MnTi(PO4)3) is closely related to the intrinsic anti-site defect (IASD), which forms during synthesis and is captured in our characterizations. Combining electrochemical analysis and spectroscopic techniques, we draw a comprehensive picture of sluggish Na+ diffusion behaviours in the IASD-affected structure during cycling, and rationalize the relationship of voltage hysteresis, phase separation and delayed charge compensation. Furthermore, a Mo-doping strategy is developed to decrease the defect concentration, which enhances the initial Coulombic efficiency from 76.2% to 85.9%. Overall, this work sheds light on the voltage hysteresis in NASICON-type cathodes and provides guidelines for designing high-performance polyanionic electrodes.

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Fig. 1: The differences between derivative anti-site defect and intrinsic anti-site defect.
Fig. 2: Voltage hysteresis and capacity loss of Na3MnTi(PO4)3.
Fig. 3: Structural characterizations of as-synthesized materials.
Fig. 4: Operando and ex situ characterizations of structural evolution and charge compensation.
Fig. 5: Effect of IASD on Na+ de-intercalation.
Fig. 6: Superior electrochemical performance of NMTP-M over NMTP.

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Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information files. Source data are provided with this paper.

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Acknowledgements

Y.-S.H. acknowledges support by the National Key Technologies R&D Program (2022YFB3807800), the National Natural Science Foundation of China (NSFC) (52122214) and the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2020006). J.Z. acknowledges support by the Beijing Natural Science Foundation (2222078) and National Natural Science Foundation of China (52072370). The authors wish to thank the support of the BL11W and BL02B02 beamlines of Shanghai Synchrotron Radiation Facility.

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Author notes

  1. These authors contributed equally: Yuan Liu, Xiaohui Rong.

Authors and Affiliations

  1. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Yuan Liu, Xiaohui Rong, Rui Bai, Ruijuan Xiao, Chunliu Xu, Chu Zhang, Qinghua Zhang, Yaxiang Lu, Liquan Chen & Yong-Sheng Hu

  2. College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing, China

    Yuan Liu, Xiaohui Rong & Yong-Sheng Hu

  3. Yangtze River Delta Physics Research Center Co. Ltd, Liyang, China

    Xiaohui Rong, Qinghua Zhang & Yong-Sheng Hu

  4. Spallation Neutron Source Science Center, Dalang, PR China

    Juping Xu & Wen Yin

  5. Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, PR China

    Juping Xu & Wen Yin

  6. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan, China

    Xinmiao Liang

  7. Huairou Division, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Yaxiang Lu & Yong-Sheng Hu

  8. CAS Key Laboratory of Green Process and Engineering, State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

    Junmei Zhao

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Contributions

Y.-S.H. and J.Z. designed and supervised the project. Y.L. synthesized, characterized (X-ray diffraction, XAS, TG, SEM, NPD, Raman) and electrochemically tested the samples and analysed the data with X.R. and R.B. X.L. performed the NMR measurements and analysis. Q.Z. performed the STEM measurements and analysis. J.X. and W.Y. performed neutron diffraction measurements and analysis. R.X. designed and performed DFT calculations and analysis. C.Z. performed the TEM and electron energy loss spectroscopy measurements and analysis. Y.L., X.R., and Y.-S.H. wrote the manuscript. All the authors participated in the discussion to improve the paper and made revisions of the whole manuscript.

Corresponding authors

Correspondence to Junmei Zhao or Yong-Sheng Hu.

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Nature Energy thanks Zdeněk Sofer, Yan Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–33, Tables 1–3, Note 1 and References.

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Liu, Y., Rong, X., Bai, R. et al. Identifying the intrinsic anti-site defect in manganese-rich NASICON-type cathodes. Nat Energy 8, 1088–1096 (2023). https://doi.org/10.1038/s41560-023-01301-z

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