Organosulfur/conducting polymer composite cathodes

II. Spectroscopic determination of the protonation and oxidation states of 2,5-dimercapto-1,3,4-thiadiazole

John M. Pope, Toshitada Sato, Eiichi Shoji, Noboru Oyama, Kevin C. White, Daniel Buttry

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

The dimercaptan 2,5-dimercapto-1,3,4-thiadiazole (DMcT) has been employed as a component in secondary lithium battery cathodes. However, spectroscopic studies of its behavior have been impeded by general uncertainty regarding its vibrational band character. The purpose of this study is to provide a spectroscopic basis for the unambiguous determination of protonation and oxidation state of DMcT. The first part of this paper is concerned with structural and spectroscopic assignment of DMcT and some derivatives. Several structural and spectroscopic assignments are intrinsically interesting, including (i) the suggestion that the thioamide-containing compounds adopt the thione tautomer structure whenever the opposite nitrogen is unsubstituted and (ii) assignment of an A1 ring mode for the first time for these compounds. The second part of this paper uses that resource to examine the in situ Raman spectroelectrochemistry of DMcT in a nonaqueous solvent. The results confirm, in part, the redox wave assignments made previously in the literature. Specifically, Raman spectroelectrochemistry of solutions of DMcT and the lithium salt of its first conjugate base (LiDMcT) show that at ca. 0.8 V LiDMcT is oxidized while DMcT is not oxidized, and that at +1.9 V both species were oxidized. Results regarding oxidation-initiated precipitation of oligomers are also reported.

Original languageEnglish (US)
JournalJournal of the Electrochemical Society
Volume149
Issue number7
DOIs
StatePublished - Jul 2002
Externally publishedYes

Fingerprint

Spectroelectrochemistry
Protonation
Conducting polymers
conducting polymers
Cathodes
cathodes
Oxidation
oxidation
composite materials
Lithium batteries
Composite materials
Oligomers
Lithium
Salts
Nitrogen
Derivatives
storage batteries
lithium batteries
tautomers
Thioamides

ASJC Scopus subject areas

  • Electrochemistry
  • Surfaces, Coatings and Films
  • Surfaces and Interfaces

Cite this

Organosulfur/conducting polymer composite cathodes : II. Spectroscopic determination of the protonation and oxidation states of 2,5-dimercapto-1,3,4-thiadiazole. / Pope, John M.; Sato, Toshitada; Shoji, Eiichi; Oyama, Noboru; White, Kevin C.; Buttry, Daniel.

In: Journal of the Electrochemical Society, Vol. 149, No. 7, 07.2002.

Research output: Contribution to journalArticle

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