4.7 Article

Reduced graphene oxide as a charge reservoir of manganese oxide: Interfacial interaction promotes charge storage property of MnOx-based micro-supercapacitors

Journal

CHEMICAL ENGINEERING JOURNAL
Volume 439, Issue -, Pages -

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2022.135569

Keywords

Reduced graphene oxide; Birnessite manganese oxide; Heterostructured film; Density functional theory calculation; Micro-supercapacitor

Funding

  1. Research and Development Program of the Korea Institute of Energy Research [C1-2404]
  2. Center for Advanced Meta-Materials (CAMM) - Ministry of Science and Information and Communication Technologies of the Republic of Korea [2019M3A6B3030636]
  3. Nano-Material Technology Development Program through the National Research Foundation of Korea (NRF) - Ministry of Science and Information and Communication Technologies of the Republic of Korea [NRF-2018M3A7B4065596]
  4. National Supercomputing Center [KSC-2020-CHA-0006, KSC-2021-CRE-0140, KSC-2021-CRE-0357]

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A hybrid film of rGO and K-MnOx has been developed to increase the energy density of micro-supercapacitors. This hybrid film exhibits high volumetric capacitance and long cycle life, serving as a stepping stone for designing novel hybrid devices with high energy storage capabilities.
Reduced graphene oxide (rGO)-based micro-supercapacitors (MSCs) have emerged as a new type of micro-energy storage device. However, the low volumetric energy density of rGO hampers the application of MSCs in mini-aturized energy storage devices. Hybridization of pseudocapacitive materials with rGO is a potential approach to increase the energy density of MSCs. Herein, a densely packed hybrid film of birnessite-type manganese oxide (K-MnOx) supported by rGO is developed, and hybrid-film-based MSCs are found to show a high volumetric capacitance (490 F/cm(3)) that is similar to 1.2 and 19 times greater than those of rGO and K-MnOx-based MSCs, respectively. A semi-permanent cycle life with capacitance retention of 97% after 10,000 cycles is observed. Moreover, a charge reservoir concept is introduced, which explains the origin of the high pseudocapacitance of the K-MnOx/rGO hybrid in a unique way. It is observed that synergistic interaction among the charge reservoir (rGO) and electron transfer channel (K-MnOx, which becomes conductive at the interface) facilitates the charging and discharging of K ions, with minimum deviation of the Mn oxidation states. This new charge reservoir concept would serve as a stepping stone toward designing novel hybrid devices with high energy storage capabilities.

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