dc.citation.endPage |
2911 |
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dc.citation.number |
10 |
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dc.citation.startPage |
2904 |
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dc.citation.title |
JOURNAL OF SOLID STATE CHEMISTRY |
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dc.citation.volume |
182 |
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dc.contributor.author |
Goodenough, John B. |
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dc.contributor.author |
Kim, Youngsik |
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dc.date.accessioned |
2023-12-22T07:39:12Z |
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dc.date.available |
2023-12-22T07:39:12Z |
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dc.date.created |
2014-10-02 |
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dc.date.issued |
2009-10 |
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dc.description.abstract |
Use of LiPF6 in EC:DEC as electrolyte has allowed electrochemical extraction of Li from LiV1-yMyS2 and LiTi1-yMyS2 (M=Cr or Fe). The data show access not only to the Ti(IV)/Ti(III) and V(IV)/V(III) redox couples, but also to the V(V)/V(IV) and Fe(III)/Fe(II) couples in these layered sulfides. However, the Cr(IV)/Cr(III) couple could not be accessed. The concept of redox-couple pinning is outlined and applied to the V(V)/V(IV) and Fe(III)/Fe(II) couples, which are pinned at the top of the S-3p bands. Holes associated with the "pinned" couples occupy orbitals of dominant S-3p character, but they have sufficient cation-3d character to prevent condensation of the holes into p-p antibonding states of disulfide bonds. Strong covalent bonding in the pinned couples creates itinerant-electron states in the partially occupied couples. Application to the metallic, ferromagnetic thiospinel Cu[Cr2]S4 favors location of the itinerant holes in states of a pinned Cu(II)/Cu(I) couple having primarily S-3p character. |
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dc.identifier.bibliographicCitation |
JOURNAL OF SOLID STATE CHEMISTRY, v.182, no.10, pp.2904 - 2911 |
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dc.identifier.doi |
10.1016/j.jssc.2009.08.005 |
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dc.identifier.issn |
0022-4596 |
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dc.identifier.scopusid |
2-s2.0-70349547127 |
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dc.identifier.uri |
https://scholarworks.unist.ac.kr/handle/201301/6816 |
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dc.identifier.url |
http://www.scopus.com/inward/record.url?partnerID=HzOxMe3b&scp=70349547127 |
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dc.identifier.wosid |
000270747800047 |
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dc.language |
영어 |
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dc.publisher |
ACADEMIC PRESS INC ELSEVIER SCIENCE |
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dc.title |
Locating redox couples in the layered sulfides with application to Cu[Cr-2]S-4 |
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dc.type |
Article |
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dc.description.journalRegisteredClass |
scopus |
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