skip to main content

DOE PAGESDOE PAGES

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

Manganese oxide (α-MnO 2) has been considered as 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 2O 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:
Report Number(s):
BNL-200057-2018-JAAM
Journal ID: ISSN 0935-9648; TRN: US1802020
Grant/Contract Number:
SC0012704; DESC0012704
Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 43; Journal ID: ISSN 0935-9648
Publisher:
Wiley
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) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
OSTI Identifier:
1425056
Alternate Identifier(s):
OSTI ID: 1398290

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., 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. 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, and Zhu, Yimei. 2017. "Lithiation Mechanism of Tunnel-Structured MnO 2 Electrode Investigated by In Situ Transmission Electron Microscopy". United States. doi: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 = {Manganese oxide (α-MnO2) has been considered as 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-MnO2 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-MnO2 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 Li2O phases with preferred orientations is demonstrated, which explains how the conversion reaction occurs in α-MnO2 material. This study provides a comprehensive understanding of the electrochemical lithiation process and mechanism of α-MnO2 material, in addition to the introduction of an improved in situ TEM biasing technique.},
doi = {10.1002/adma.201703186},
journal = {Advanced Materials},
number = 43,
volume = 29,
place = {United States},
year = {2017},
month = {10}
}

Works referenced in this record:

Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries
journal, September 2000
  • Poizot, P.; Laruelle, S.; Grugeon, S.
  • Nature, Vol. 407, Issue 6803, p. 496-499
  • DOI: 10.1038/35035045

In situ fabrication of porous-carbon-supported α-MnO2 nanorods at room temperature: application for rechargeable Li–O2 batteries
journal, January 2013
  • Qin, Yan; Lu, Jun; Du, Peng
  • Energy & Environmental Science, Vol. 6, Issue 2, p. 519-531
  • DOI: 10.1039/c2ee23621d

Reversible Sodium Ion Insertion in Single Crystalline Manganese Oxide Nanowires with Long Cycle Life
journal, June 2011
  • Cao, Yuliang; Xiao, Lifen; Wang, Wei
  • Advanced Materials, Vol. 23, Issue 28, p. 3155-3160
  • DOI: 10.1002/adma.201100904

On the Origin of the Extra Electrochemical Capacity Displayed by MO/Li Cells at Low Potential
journal, January 2002
  • Laruelle, S.; Grugeon, S.; Poizot, P.
  • Journal of The Electrochemical Society, Vol. 149, Issue 5, p. A627-A634
  • DOI: 10.1149/1.1467947