A study of binary iron/lithium organometallic complexes as single source precursors to solid state cathode materials for potential Li ion battery application

Jayaprakash Khanderi, Jörg J. Schneider

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

Solid state and solution phase decomposition of organometallic half sandwich and sandwich complexes of type [CpFeCODLi × DME] 1, [CpFeCODLi × TMEDA] 2 and [(Cp)2FeLi2 × 2 TMEDA] 3 (Cp = cyclopentadienyl, COD = 1,5-cyclooctadiene, DME = dimethoxyethane, TMEDA = tetramethylethylenediamine) derived from ferrocene, yield different kinds of lithium ferrites under oxidative and inert conditions. Thermogravimetry (TG) and TG coupled mass spectrometry of these compounds indicate that the decomposition begins above 170 °C for 1, 185 °C for 2 and 190 °C for 3 with removal of all the organic ligands. In the absence of oxygen, compounds 1, 2 and 3 decompose to a mixture of Fe, Fe3C and Li2O/Li 2CO3 at temperatures above 200 °C. Amorphous α-LiFeO2 is formed in the temperature range of 200-400 °C in the presence of oxygen. Crystalline α-LiFeO2 is formed only above 400 °C using 1. Elemental analysis of the LiFeO2 obtained from 1 indicates a drastic decrease in the carbon and hydrogen content with the increase in the oxidation temperature. XRD reveals the presence of Li 2CO3 as second phase formed for precursors 1, 2, and 3 under oxidative conditions. Solution phase decomposition of 2 and 3 in the absence of oxygen followed by annealing at 600 °C yields Li 2Fe3O5, Li5FeO4 and Fe3C depending on the solvent to precursor ratio in contrast to the α-LiFeO2 phase formed under pure solid state decomposition conditions. However, all lithium ferrites (Li2Fe3O 5, Li5FeO4) are converted to α-LiFeO 2 when oxidized above 500 °C. The α-LiFeO2 products were further characterized by IR, XPS, and TEM. Electrochemical analysis of the α-LiFeO2 was performed, showing a moderate initial capacity of 13 mAh/g.

Original languageEnglish (US)
Pages (from-to)254-259
Number of pages6
JournalInorganica Chimica Acta
Volume370
Issue number1
DOIs
StatePublished - May 15 2011

Keywords

  • Electrochemistry
  • Ferrite
  • Iron
  • Lithium
  • Organometallic single source precursor decomposition

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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