Synthesis, redox potential evaluation and electrochemical characteristics of NASICON-related-3D framework compounds

K. S. Nanjundaswamy, A. K. Padhi, J. B. Goodenough, S. Okada, H. Ohtsuka, H. Arai, J. Yamaki

Research output: Contribution to journalArticle

278 Citations (Scopus)

Abstract

The framework compounds M2(SO4)3 with M = (Ti Fe), (V Fe), Fe and LixM2(PO4)3 with M = Ti, (V Fe), Fe, were synthesized and electrochemically characterized by the coin-cell method. Use of larger (XO4)n- polyanions not only allows fast Li+-ion conduction in an open three-dimensional framework that is selective for the working alkali ion on discharge; it also stabilizes operative redox potentials Fe3+/Fe2+, Ti4+/Ti3+ and V3+/V2+ that give open-circuit voltages Voc > 2.5 Vas well as access to V4+/V3+, Ti3+/Ti2+ and Fe2+/Fe+ couples. Separation of the V4+/V3+ and V3+/V2+ couples were found to be 2.0 V. Fe2(SO4)3 has both monoclinic and rhombohedral modifications that give a flat open-circuit voltage Voc = 3.6 V versus Li and a reversible capacity for ∼ 1.8 lithium atoms per formula unit. LixFe2(SO4)3 shows an abrupt voltage drop occurring for x > 2 that can be held in check by the addition of buffers such as Li3Fe2(PO4)3, FeV(SO4)3 and LiTi2(PO4)3. Changing the polyanion group from (SO4)2- to (PO4)3- in these framework compounds decreases the redox potentials from 3.2 to 2.5 V for the Ti4+/Ti3+ couple, 2.5 to 1.7 V for the V3+/V2+ couple and 3.6 to 2.8 V for the Fe3+/Fe2+ couple. Comparative advantages and disadvantages of framework cathodes for Li rechargeable battery applications are discussed.

Original languageEnglish
Pages (from-to)1-10
Number of pages10
JournalSolid State Ionics
Volume92
Issue number1-2
Publication statusPublished - Nov 1 1996
Externally publishedYes

    Fingerprint

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Nanjundaswamy, K. S., Padhi, A. K., Goodenough, J. B., Okada, S., Ohtsuka, H., Arai, H., & Yamaki, J. (1996). Synthesis, redox potential evaluation and electrochemical characteristics of NASICON-related-3D framework compounds. Solid State Ionics, 92(1-2), 1-10.