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Title: Ordering Heterogeneity of [MnO 6] Octahedra in Tunnel-Structured MnO 2 and Its Influence on Ion Storage

Abstract

[MnO 6] octahedra are the structural units for a large family of manganese dioxides (MnO 2) possessing one-dimensional tunnel structures with extensive applications in catalysis and energy storage. Despite the long-range [MnO 6] ordering confirmed by conventional diffraction tools, surprisingly, the functional properties of a specific MnO 2 tunnel phase still vary significantly in literature with unclear structural origins. Here, we demonstrate the existence of tunnel heterogeneity featuring localized tunnel intergrowths within single MnO 2 nanoparticles via atomically resolved imaging. The degree of tunnel heterogeneity increases with the size increase of tunnels from β-MnO 2 (1 × 1 tunnel) to α-MnO 2 (2 × 2 tunnel), and to todorokite MnO 2 (3 × 3 tunnel). Furthermore, the tunnel heterogeneity within one MnO 2 nanoparticle significantly affects the energy storage kinetics even down to sub-nanometer scale. Furthermore these findings are expected to call for renewed attention to the controlled synthesis of homogeneous tunnel-specific phases with predictable properties and to yield a more precise structure-property relationship in polymorphic materials.

Authors:
 [1];  [2];  [3];  [4];  [4];  [4];  [4];  [2];  [3];  [4]; ORCiD logo [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Illinois at Chicago, Chicago, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Drexel Univ., Philadelphia, PA (United States)
  4. Univ. of Illinois at Chicago, Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); Directorate for Mathematical and Physical Sciences Division of Materials Research (MPS-DMR); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1505609
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Joule
Additional Journal Information:
Journal Volume: 3; Journal Issue: 2; Journal ID: ISSN 2542-4351
Publisher:
Elsevier - Cell Press
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; atomic resolution; energy storage; manganese dioxidetunnel; structure heterogeneity; tunnel structure

Citation Formats

Yuan, Yifei, Liu, Cong, Byles, Bryan W., Yao, Wentao, Song, Boao, Cheng, Meng, Huang, Zhennan, Amine, Khalil, Pomerantseva, Ekaterina, Shahbazian-Yassar, Reza, and Lu, Jun. Ordering Heterogeneity of [MnO6] Octahedra in Tunnel-Structured MnO2 and Its Influence on Ion Storage. United States: N. p., 2018. Web. doi:10.1016/j.joule.2018.10.026.
Yuan, Yifei, Liu, Cong, Byles, Bryan W., Yao, Wentao, Song, Boao, Cheng, Meng, Huang, Zhennan, Amine, Khalil, Pomerantseva, Ekaterina, Shahbazian-Yassar, Reza, & Lu, Jun. Ordering Heterogeneity of [MnO6] Octahedra in Tunnel-Structured MnO2 and Its Influence on Ion Storage. United States. doi:10.1016/j.joule.2018.10.026.
Yuan, Yifei, Liu, Cong, Byles, Bryan W., Yao, Wentao, Song, Boao, Cheng, Meng, Huang, Zhennan, Amine, Khalil, Pomerantseva, Ekaterina, Shahbazian-Yassar, Reza, and Lu, Jun. Tue . "Ordering Heterogeneity of [MnO6] Octahedra in Tunnel-Structured MnO2 and Its Influence on Ion Storage". United States. doi:10.1016/j.joule.2018.10.026.
@article{osti_1505609,
title = {Ordering Heterogeneity of [MnO6] Octahedra in Tunnel-Structured MnO2 and Its Influence on Ion Storage},
author = {Yuan, Yifei and Liu, Cong and Byles, Bryan W. and Yao, Wentao and Song, Boao and Cheng, Meng and Huang, Zhennan and Amine, Khalil and Pomerantseva, Ekaterina and Shahbazian-Yassar, Reza and Lu, Jun},
abstractNote = {[MnO6] octahedra are the structural units for a large family of manganese dioxides (MnO2) possessing one-dimensional tunnel structures with extensive applications in catalysis and energy storage. Despite the long-range [MnO6] ordering confirmed by conventional diffraction tools, surprisingly, the functional properties of a specific MnO2 tunnel phase still vary significantly in literature with unclear structural origins. Here, we demonstrate the existence of tunnel heterogeneity featuring localized tunnel intergrowths within single MnO2 nanoparticles via atomically resolved imaging. The degree of tunnel heterogeneity increases with the size increase of tunnels from β-MnO2 (1 × 1 tunnel) to α-MnO2 (2 × 2 tunnel), and to todorokite MnO2 (3 × 3 tunnel). Furthermore, the tunnel heterogeneity within one MnO2 nanoparticle significantly affects the energy storage kinetics even down to sub-nanometer scale. Furthermore these findings are expected to call for renewed attention to the controlled synthesis of homogeneous tunnel-specific phases with predictable properties and to yield a more precise structure-property relationship in polymorphic materials.},
doi = {10.1016/j.joule.2018.10.026},
journal = {Joule},
issn = {2542-4351},
number = 2,
volume = 3,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
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