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Lithium Migration Pathways and van der Waals Effects in the LiFeSO4OH Battery Material

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Department of Chemistry, University of Bath, Bath BA2 7AY, United Kingdom
Institut de Minéralogie, de Physique des Matériaux, et de Cosmochimie (IMPMC), Sorbonne Universités—UPMC Univ Paris 06, UMR CNRS 7590, Muséum National d’Histoire Naturelle, IRD UMR 206, 4 Place Jussieu, F-75005 Paris, France
§ Réseau sur le Stockage Electrochimique de l’Energie (RS2E), FR CNRS 3459, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France
*(M.S.I.) E-mail: [email protected]
Cite this: Chem. Mater. 2014, 26, 12, 3672–3678
Publication Date (Web):May 20, 2014
Copyright © 2014 American Chemical Society

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    Layered LiFeSO4OH has recently attracted interest as a sustainable cathode material for rechargeable lithium batteries that offers favorable synthesis and processing routes. Here, the defect chemistry, lithium-ion transport pathways, and cell voltages of layered LiFeSO4OH are investigated by atomistic modeling and density functional theory (DFT) methods and compared with the tavorite polymorph. The results indicate that the layered phase exhibits two-dimensional (2D) lithium-ion diffusion with low activation energies of ∼0.2 eV for long-range transport within the bc-plane, which is important for good rate capability. The tavorite phase also shows 2D lithium-ion diffusion but with higher activation energies of ∼0.7 eV. Using DFT+U techniques the experimental voltage and structural parameters are accurately reproduced for the tavorite polymorph. For the layered structure, similar accuracy in both cell voltage and structure can only be obtained if a van der Waals functional is included in the DFT methodology to account for the interlayer binding.

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    Interlayer binding energy curve for layered FeSO4OH. Voltages computed with G06 empirical vdW correction. Structural changes during AIMD annealing. This material is available free of charge via the Internet at

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