Electronic And Geometric Structures Of Rechargeable Lithium Manganese Sulfate Li2mn(So4)(2) Cathode

ACS omega(2019)

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摘要
Here, we report the use of Li2Mn(SO4)(2) as a potential energy storage material and describe its route of synthesis and structural characterization over one electrochemical cycle. Li2Mn(SO4)(2) is synthesized by ball milling of MnSO4 center dot H2O and Li2SO4 center dot H2O and characterized using a suite of techniques, in particular, ex situ X-ray diffraction, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy on the Mn and S K-edges to investigate the electronic and local geometry around the absorbing atoms. The prepared Li2Mn(SO4)(2) electrodes undergo electrochemical cycles to different potential points on the charge-discharge curve and are then extracted from the cells at these points for ex situ structural analysis. Analysis of X-ray absorption spectroscopy (both near and fine structure part of the data) data suggests that there are minimal changes to the oxidation state of Mn and S ions during charge-discharge cycles. However, X-ray photoelectron spectroscopy analysis suggests that there are changes in the oxidation state of Mn, which appears to be different from the conclusion drawn from X-ray absorption spectroscopy. This difference in results during cycling can thus be attributed to electrochemical reactions being dominant at the surface of the Li2Mn(SO4)(2) particles rather than in the bulk.
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