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Title: Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy

Abstract

Abstract Manganese oxide (α‐MnO 2 ) has been considered a promising energy material, including as a lithium‐based battery electrode candidate, due to its environmental friendliness. Thanks to its unique 1D [2 × 2] tunnel structure, α‐MnO 2 can be applied to a cathode by insertion reaction and to an anode by conversion reaction in corresponding voltage ranges, in a lithium‐based battery. Numerous reports have attributed its remarkable performance to its unique tunnel structure; however, the precise electrochemical reaction mechanism remains unknown. In this study, finding of the lithiation mechanism of α‐MnO 2 nanowire by in situ transmission electron microscopy (TEM) is reported. By elaborately modifying the existing in situ TEM experimental technique, rapid lithium‐ion diffusion through the tunnels is verified. Furthermore, by tracing the full lithiation procedure, the evolution of the MnO intermediate phase and the development of the MnO and Li 2 O phases with preferred orientations is demonstrated, which explains how the conversion reaction occurs in α‐MnO 2 material. This study provides a comprehensive understanding of the electrochemical lithiation process and mechanism of α‐MnO 2 material, in addition to the introduction of an improved in situ TEM biasing technique.

Authors:
 [1];  [2];  [2];  [3];  [3];  [3];  [4];  [5];  [2]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Seoul National Univ. (Korea, Republic of)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Stony Brook Univ., NY (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
  5. Seoul National Univ. (Korea, Republic of)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1425056
Alternate Identifier(s):
OSTI ID: 1398290
Report Number(s):
BNL-200057-2018-JAAM
Journal ID: ISSN 0935-9648; TRN: US1802020
Grant/Contract Number:  
SC0012704; DESC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 43; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Lee, Seung-Yong, Wu, Lijun, Poyraz, Altug S., Huang, Jianping, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., Kim, Miyoung, and Zhu, Yimei. Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy. United States: N. p., 2017. Web. doi:10.1002/adma.201703186.
Lee, Seung-Yong, Wu, Lijun, Poyraz, Altug S., Huang, Jianping, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., Kim, Miyoung, & Zhu, Yimei. Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy. United States. https://doi.org/10.1002/adma.201703186
Lee, Seung-Yong, Wu, Lijun, Poyraz, Altug S., Huang, Jianping, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., Kim, Miyoung, and Zhu, Yimei. 2017. "Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy". United States. https://doi.org/10.1002/adma.201703186. https://www.osti.gov/servlets/purl/1425056.
@article{osti_1425056,
title = {Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy},
author = {Lee, Seung-Yong and Wu, Lijun and Poyraz, Altug S. and Huang, Jianping and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Kim, Miyoung and Zhu, Yimei},
abstractNote = {Abstract Manganese oxide (α‐MnO 2 ) has been considered a promising energy material, including as a lithium‐based battery electrode candidate, due to its environmental friendliness. Thanks to its unique 1D [2 × 2] tunnel structure, α‐MnO 2 can be applied to a cathode by insertion reaction and to an anode by conversion reaction in corresponding voltage ranges, in a lithium‐based battery. Numerous reports have attributed its remarkable performance to its unique tunnel structure; however, the precise electrochemical reaction mechanism remains unknown. In this study, finding of the lithiation mechanism of α‐MnO 2 nanowire by in situ transmission electron microscopy (TEM) is reported. By elaborately modifying the existing in situ TEM experimental technique, rapid lithium‐ion diffusion through the tunnels is verified. Furthermore, by tracing the full lithiation procedure, the evolution of the MnO intermediate phase and the development of the MnO and Li 2 O phases with preferred orientations is demonstrated, which explains how the conversion reaction occurs in α‐MnO 2 material. This study provides a comprehensive understanding of the electrochemical lithiation process and mechanism of α‐MnO 2 material, in addition to the introduction of an improved in situ TEM biasing technique.},
doi = {10.1002/adma.201703186},
url = {https://www.osti.gov/biblio/1425056}, journal = {Advanced Materials},
issn = {0935-9648},
number = 43,
volume = 29,
place = {United States},
year = {Fri Oct 06 00:00:00 EDT 2017},
month = {Fri Oct 06 00:00:00 EDT 2017}
}

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Works referenced in this record:

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Asynchronous Crystal Cell Expansion during Lithiation of K + -Stabilized α-MnO 2
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Works referencing / citing this record:

Nanowires in Energy Storage Devices: Structures, Synthesis, and Applications
journal, October 2018


In situ TEM study of lithiation into a PPy coated α-MnO 2 /graphene foam freestanding electrode
journal, January 2018


Highly effective fabrication of two dimensional metal oxides as high performance lithium storage anodes
journal, January 2019