Origin of improved electrochemical activity of β-MnO2 nanorods: Effect of the Mn valence in the precursor on the crystal structure and electrode activity of manganates

In Young Kim, Hyung Wook Ha, Tae Woo Kim, Younkee Paik, Jin Ho Choy, Seong Ju Hwang

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22 Citations (Scopus)

Abstract

1D nanorods/nanowires of manganese oxides with different crystal structures and morphologies were prepared and characterized to understand the influence of the Mn valence in the solid-state precursor on the electrochemical activity of these nanomaterials and to elucidate the mechanism responsible for the excellent activity of β-MnO2 nanorods as well. According to powder X-ray diffraction analyses, treating manganese oxide precursors that have an oxidation state of ≤+3 with persulfate ions under hydrothermal conditions yields manganese oxides with the β-MnO2 structure. In contrast, the use of a LiMn2O4 precursor with a higher Mn valence leads to the formation of the α-MnO2-structured manganese oxide. Electron microscopic studies clearly show a 1D nanorod-type morphology for the β-MnO2 material, whereas a 1D nanowire-type morphology with a higher aspect ratio is observed for the α-MnO2 material. The diameter of the β-MnO2 nanorods decreases as the Mn valence in the precursors becomes smaller. According to electrochemical measurements, the formation of nanorods dramatically improves the electrode performance of the β-MnO2 phase. This compares with a relatively weak performance enhancement for the α- and δ-MnO2 phases upon the nanowire formation. The optimum electrode property results from the smaller β-MnO2 nanorods prepared with the MnO precursor. 7Li magic angle spinning nuclear magnetic resonance spectroscopy clearly demonstrates that Li+ ions in the lithiated β-MnO2 phase are adsorbed mainly on the sample surface. On the basis of this finding, we attribute the improved electrode performance of the β-MnO2 nanorods to their expanded surface area.

Original languageEnglish
Pages (from-to)21274-21282
Number of pages9
JournalJournal of Physical Chemistry C
Volume113
Issue number51
DOIs
Publication statusPublished - 2009

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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