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Origin of unusual spinel-to-layered phase transformation by crystal water

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Abstract

It is well known that many layered transition metal oxides can transform into a spinel structure upon repeated battery cycling, but a phase transition in the opposite direction is rare. Recently, the transformation from spinel Mn3O4 to layered MnO2 was observed during the operation of a Mg battery in aqueous conditions, resulting in high performance Mg batteries. We hereby use ab initio calculations to unveil the mechanism by which crystal water plays a critical role in this unique transformation. Once inserted into the spinel form, a water molecule donates an electron, offering a key structural and thermodynamic driving force to initiate the transformation process. These crystal water molecules then get favorably clustered into a planar form in the layered structure and act as a stabilizing agent for birnessite. Kinetically, the inserted crystal water dramatically promotes the necessary rearrangement of Mn during the transition by lowering the activation barrier by >2 eV. The present structural, thermodynamic and kinetic understanding of the crystal water-driven phase transition provides novel insights to further the design of related low dimensional hydrated materials for multi-valent cathodes.

Graphical abstract: Origin of unusual spinel-to-layered phase transformation by crystal water

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Publication details

The article was received on 20 Sep 2017, accepted on 24 Oct 2017 and first published on 24 Oct 2017


Article type: Edge Article
DOI: 10.1039/C7SC04114D
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY license
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    Origin of unusual spinel-to-layered phase transformation by crystal water

    E. Yang, H. Kim, S. Kim, I. Kim, J. Kim, H. Ji, J. W. Choi and Y. Jung, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C7SC04114D

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