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Issue 34, 2015
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Unusual Mn coordination and redox chemistry in the high capacity borate cathode Li7Mn(BO3)3

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Abstract

The recently discovered lithium-rich cathode material Li7Mn(BO3)3 has a high theoretical capacity and an unusual tetrahedral Mn2+ coordination. Atomistic simulation and density functional theory (DFT) techniques are employed to provide insights into the defect and redox chemistry, the structural changes upon lithium extraction and the mechanisms of lithium ion diffusion. The most favourable intrinsic defects are Li/Mn anti-site pairs, where Li and Mn ions occupy interchanged positions, and Li Frenkel defects. DFT calculations reproduce the experimental cell voltage and confirm the presence of the unusually high MnV redox state, which corresponds to a theoretical capacity of nearly 288 mA h g−1. The ability to reach the high manganese oxidation state is related to both the initial tetrahedral coordination of Mn and the observed distortion/tilting of the BO3 units to accommodate the contraction of the Mn–O bonds upon oxidation. Molecular dynamics (MD) simulations indicate fast three-dimensional lithium diffusion in line with the good rate performance observed.

Graphical abstract: Unusual Mn coordination and redox chemistry in the high capacity borate cathode Li7Mn(BO3)3

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Publication details

The article was received on 11 May 2015, accepted on 29 Jul 2015 and first published on 29 Jul 2015


Article type: Paper
DOI: 10.1039/C5CP02711J
Citation: Phys. Chem. Chem. Phys., 2015,17, 22259-22265
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    Unusual Mn coordination and redox chemistry in the high capacity borate cathode Li7Mn(BO3)3

    J. Roos, C. Eames, S. M. Wood, A. Whiteside and M. Saiful Islam, Phys. Chem. Chem. Phys., 2015, 17, 22259
    DOI: 10.1039/C5CP02711J

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