Effect of structure on the Fe3+/Fe2+ redox couple in iron phosphates

A. K. Padhi, K. S. Nanjundaswamy, C. Masquelier, S. Okada, J. B. Goodenough

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1196 Citations (Scopus)


To understand the role of structure on the position of the octahedral Fe3+/Fe2+ redox couple in compounds having the same polyanions, four iron phosphates: Li3Fe2(PO4)3, LiFeP2O7, Fe4(P2O7)3, and LiFePO4 were investigated. They vary in structure as well as in the manner in which the octahedral iron atoms are linked to each other. The Fe3+/Fe2+ redox couple in the above compounds lies at 2.8, 2.9, 3.1, and 3.5 eV, respectively, below the Fermi level of lithium. The reason for the difference in the position of the redox couples is related to changes in the P-O bond lengths as well as to changes in the crystalline electric field at the iron sites.

Original languageEnglish
Pages (from-to)1609-1613
Number of pages5
JournalJournal of the Electrochemical Society
Issue number5
Publication statusPublished - May 1997
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics
  • Materials Chemistry
  • Surfaces, Coatings and Films
  • Electrochemistry
  • Renewable Energy, Sustainability and the Environment


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