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

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

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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

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Open circuit voltage
Ions
Secondary batteries
evaluation
Alkalies
synthesis
Lithium
Buffers
open circuit voltage
Cathodes
Atoms
electric batteries
alkalies
ions
lithium
buffers
cathodes
polyanions
Oxidation-Reduction
conduction

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.

Synthesis, redox potential evaluation and electrochemical characteristics of NASICON-related-3D framework compounds. / Nanjundaswamy, K. S.; Padhi, A. K.; Goodenough, J. B.; Okada, Shigeto; Ohtsuka, H.; Arai, H.; Yamaki, J.

In: Solid State Ionics, Vol. 92, No. 1-2, 01.11.1996, p. 1-10.

Research output: Contribution to journalArticle

Nanjundaswamy, KS, Padhi, AK, Goodenough, JB, 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, vol. 92, no. 1-2, pp. 1-10.
Nanjundaswamy KS, Padhi AK, Goodenough JB, Okada S, Ohtsuka H, Arai H et al. Synthesis, redox potential evaluation and electrochemical characteristics of NASICON-related-3D framework compounds. Solid State Ionics. 1996 Nov 1;92(1-2):1-10.
Nanjundaswamy, K. S. ; Padhi, A. K. ; Goodenough, J. B. ; Okada, Shigeto ; Ohtsuka, H. ; Arai, H. ; Yamaki, J. / Synthesis, redox potential evaluation and electrochemical characteristics of NASICON-related-3D framework compounds. In: Solid State Ionics. 1996 ; Vol. 92, No. 1-2. pp. 1-10.
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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.",
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N2 - 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.

AB - 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.

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