Jump to main content
Jump to site search

Issue 8, 2019
Previous Article Next Article

Tuning polaronic redox behavior in olivine phosphate

Author affiliations


In order to understand and improve the conductivity of LiFePO4, lots of attempts have been made both experimentally and theoretically. Here we performed hybrid density functional theory calculations to systematically investigate the electronic structures with polaronic redox behavior of polyanionic intercalation compounds similar to LiFePO4, such as in XMPO4 (X = Li, Na; M = Mn, Fe, Co, Ni). It is proved that the replacement of Li ions does not eliminate the polaronic redox behavior of Fe ions during delithiation and hence does not lead to a significant improvement in electronic conductivity. By contrast, replacing Fe with Mn, Co or Ni can tune the polaronic redox behavior during delithiation by varying degrees. For Ni, the polaronic redox behavior has almost disappeared, and band gaps disappear during delithiation, indicating a better electronic conductivity. For Mn or Co, the polaronic redox behavior is still obvious with little improvement in the electronic conductivity. This study provides important clues to improve the electronic conductivity of LiFePO4-like cathode materials.

Graphical abstract: Tuning polaronic redox behavior in olivine phosphate

Back to tab navigation

Supplementary files

Publication details

The article was received on 28 Sep 2018, accepted on 31 Jan 2019 and first published on 31 Jan 2019

Article type: Paper
DOI: 10.1039/C8CP06083E
Citation: Phys. Chem. Chem. Phys., 2019,21, 4578-4583

  •   Request permissions

    Tuning polaronic redox behavior in olivine phosphate

    Y. Gu, M. Weng, G. Teng, H. Zeng, J. Jie, W. Xiao, J. Zheng and F. Pan, Phys. Chem. Chem. Phys., 2019, 21, 4578
    DOI: 10.1039/C8CP06083E

Search articles by author