Possible correlation between enthalpies of formation and redox potentials in LiMSO4OH (M = Co, Fe, Mn), Li-ion polyanionic battery cathode materials

A. V. Radha, C. V. Subban, M. L. Sun, J. M. Tarascon, A. Navrotsky

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

The thermodynamic stabilities of lithium hydroxysulfates of general formula LiMSO4OH (M = Co, Fe, Mn) with layered and tavorite structures have been investigated using isothermal acid solution calorimetry. These compounds have been explored as sustainable F-free alternatives to F-based flurosulfate cathode materials. The energetic trends for layered LiMSO4OH (M = Co, Fe and Mn) samples generally showed a decrease in stability with an increase in ionic radius (Co2+ to Mn2+), reflecting weaker M-O bonds and increasing structural distortions. The low symmetry tavorite LiFeSO 4OH with a structure containing corner-shared octahedral chains is less stable than layered LiFeSO4OH with a more symmetric edge-shared octahedral structure. Structural distortions within the metal octahedra as well as changes in sulfate bonding and symmetry of the SO42- groups appear to control the thermodynamic and electrochemical behavior of LiMSO4OH (M = Co, Fe and Mn) materials. Both redox potential and thermodynamic stability of layered LiMSO4OH (M = Co, Fe and Mn) can be correlated to the lowering of the sulfate bonding symmetry in the structure from C3v to C2v.

Original languageEnglish (US)
Pages (from-to)6887-6894
Number of pages8
JournalJournal of Materials Chemistry A
Volume2
Issue number19
DOIs
StatePublished - May 21 2014
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)

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