Unveiling Surface Redox Charge Storage of Interacting Two-Dimensional Hetero-Nanosheets in Hierarchical Architectures

Mahmood, Qasim; Bak, Seong-Min; Kim, Min G.; Yun, Sol; Yang, Xiao-Qing; Shin, Hyeon S.; Kim, Woo S.; Braun, Paul V.; Park, Ho S.

doi:10.1021/nl504200y

Title: Unveiling Surface Redox Charge Storage of Interacting Two-Dimensional Hetero-Nanosheets in Hierarchical Architectures

Journal Article · Tue Mar 03 00:00:00 EST 2015 · Nano Letters

DOI:https://doi.org/10.1021/nl504200y· OSTI ID:1176999

Mahmood, Qasim ^[1]; Bak, Seong-Min ^[2]; Kim, Min G. ^[3]; Yun, Sol ^[4]; Yang, Xiao-Qing ^[2]; Shin, Hyeon S. ^[5]; Kim, Woo S. ^[1]; Braun, Paul V. ^[6]; Park, Ho S. ^[4]

Department of Chemical Engineering, College of Engineering, Kyung Hee University (Republic of Korea)
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Beamline Research Division, Pohang Accelerator Laboratory, Pohang (Republic of Korea)
School of Chemical Engineering, Sungkyunkwan University (SKKU), Suwon (Republic of Korea)
Department of Energy Engineering, Department of Chemistry, and Low Dimensional Carbon Materials Center, Ulsan National Institute of Science and Technology(UNIST) (Republic of Korea)
Department of Materials Science and Engineering Materials Research Laboratory and Beckman Institute, University of Illinois at Urbana−Champaign, Urbana, Illinois (United States)

Two-dimensional (2D) heteronanosheets are currently the focus of intense study due to the unique properties that emerge from the interplay between two low-dimensional nanomaterials with different properties. However, the properties and new phenomena based on the two 2D heteronanosheets interacting in a 3D hierarchical architecture have yet to be explored. Here, we unveil the surface redox charge storage mechanism of surface-exposed WS2 nanosheets assembled in a 3D hierarchical heterostructure using in situ synchrotron X-ray absorption and Raman spectroscopic methods. The surface dominating redox charge storage of WS2 is manifested in a highly reversible and ultrafast capacitive fashion due to the interaction of heteronanosheets and the 3D connectivity of the hierarchical structure. In contrast, compositionally identical 2D WS2 structures fail to provide a fast and high capacitance with different modes of lattice vibration. The distinctive surface capacitive behavior of 3D hierarchically structured heteronanosheets is associated with rapid proton accommodation into the in-plane W–S lattice (with the softening of the E2g bands), the reversible redox transition of the surface-exposed intralayers residing in the electrochemically active 1T phase of WS2 (with the reversible change in the interatomic distance and peak intensity of W–W bonds), and the change in the oxidation state during the proton insertion/deinsertion process. This proposed mechanism agrees with the dramatic improvement in the capacitive performance of the two heteronanosheets coupled in the hierarchical structure.

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: SC00112704

OSTI ID:: 1176999

Report Number(s):: BNL-107668-2015-JA; R&D Project: MA453MAEA; VT1201000

Journal Information:: Nano Letters, Vol. 15; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 72 works

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Title: Unveiling Surface Redox Charge Storage of Interacting Two-Dimensional Hetero-Nanosheets in Hierarchical Architectures

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