4.7 Article

The supercapacitor electrode properties and energy storage mechanism of binary transition metal sulfide MnCo2S4 compared with oxide MnCo2O4 studied using in situ quick X-ray absorption spectroscopy

Journal

MATERIALS CHEMISTRY FRONTIERS
Volume 5, Issue 13, Pages 4937-4949

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1qm00222h

Keywords

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Funding

  1. NSRRC
  2. Ministry of Science and Technology of the Republic of China [MOST-106-2221-E-213-002-MY3, MOST-109-2221-E-213-002-MY3, MOST-108-2113-M-213-004, MOST-109-2113-M-213-001]

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The study found that binary transition metal sulfide MCS electrode has large areal capacity, good rate capability, and cycling stability. Through X-ray absorption spectroscopy analysis, it was discovered that the breaking of Mn-S/Co-S bonds in the MCS electrode produced active sites, significantly enhancing its capacitive performance.
Binary transition-metal sulfide MnCo2S4 (MCS) and oxide MnCo2O4 (MCO) nanowires grown on nickel foam were prepared with facile hydrothermal method. The MCS electrode not only exhibits a large areal capacity, 1.17 mA h cm(-2) at current density 3 mA cm(-2) but also shows great rate capability and cycling stability in an alkaline electrolyte. In situ quick X-ray absorption spectroscopy of the Mn K-edge and Co K-edge of MCS demonstrate that both average valence states of elements Mn and Co show a notable change from the faradaic pseudocapacitance, inferring a synergistic effect of two elements. Based on a Co K-edge and Mn K-edge extended X-ray absorption fine structure analysis of MCS, some Mn-S/Co-S bonds on the surface of electrode are broken and then become active sites, which can react with hydroxide ions. Besides a synergistic effect of two elements, the active sites arising from the broken Mn-S/Co-S bonds hence enhance significantly the capacitive performance of the MCS electrode. Our work provides new insight into the electrochemical mechanism and the main difference for supercapacitor performance between MCS and the corresponding oxide MCO electrodes. These results demonstrate a different mechanism for binary transition metal sulfide and oxide in electrochemical reaction of energy storage.

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