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Issue 19, 2014
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Possible correlation between enthalpies of formation and redox potentials in LiMSO4OH (M = Co, Fe, Mn), Li-ion polyanionic battery cathode materials

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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 LiFeSO4OH 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.

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

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Article information


Submitted
31 Dec 2013
Accepted
19 Mar 2014
First published
27 Mar 2014

J. Mater. Chem. A, 2014,2, 6887-6894
Article type
Paper

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 and A. Navrotsky, J. Mater. Chem. A, 2014, 2, 6887
DOI: 10.1039/C3TA15457B

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