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Title: Dynamic study of (De)sodiation in alpha-MnO 2 nanowires

Abstract

In this report, the electrochemical sodiation and desodiation in single crystalline alpha-MnO 2 nanowires are studied dynamically at both single particle level using in situ transmission electron microscopy (TEM) and bulk level using in situ synchrotron X-ray. The TEM results suggest that the first sodiation process starts with tunnel-based Na + intercalation, experiences the formation of Na 0.5MnO 2 as a result of tunnel degradation, and ends with the Mn 2O 3 phase. The inserted Na + can be partially extracted out of the sodiated products, and the following cycles are dominated by the reversible conversion reaction between Na 0.5MnO 2 and Mn 2O 3. The Mn valence evolution inside a cycling coin using alpha-MnO 2 nanowire electrode also exhibits partially reversible characteristic, agreeing well with the in situ TEM analysis. The sodiation is compared with lithiation in the same alpha-MnO 2 nanowires. Both Na + and Li + interact with the tunneled structure via a similar tunnel -driven intercalation mechanism before Mn 4+ is reduced to Mn 3.5+. For the following deep insertion, the tunnels survive up. to LiMnO 2 (Mn3+) during lithiation, while the sodiation proceeds via a different mechanism that involves obvious phase transition and fast tunnelmore » degradation after Mn's valence is below 3.5+. The difference in charge carrier insertion mechanisms can be ascribed to the strong interaction between the tunnel frame and inserted Na + possessing a larger ionic size than inserted Li +.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [2];  [2];  [2];  [2];  [6]
  1. Michigan Technological Univ., Houghton, MI (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Michigan Technological Univ., Houghton, MI (United States); Shandong Univ., Jinan (China)
  4. Michigan Technological Univ., Houghton, MI (United States)
  5. Univ. of Illinois, Chicago, IL (United States)
  6. Michigan Technological Univ., Houghton, MI (United States); Univ. of Illinois, Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1247154
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 19; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; 77 NANOSCIENCE AND NANOTECHNOLOGY; Alpha-MnO2; In situ TEM; Mn valence; Sodium ion battery; Tunnel

Citation Formats

Yuan, Yifei, Ma, Lu, He, Kun, Yao, Wentao, Nie, Anmin, Bi, Xuanxuan, Amine, Khalil, Wu, Tianpin, Lu, Jun, and Shahbazian-Yassr, Reza. Dynamic study of (De)sodiation in alpha-MnO2 nanowires. United States: N. p., 2016. Web. doi:10.1016/j.nanoen.2015.11.028.
Yuan, Yifei, Ma, Lu, He, Kun, Yao, Wentao, Nie, Anmin, Bi, Xuanxuan, Amine, Khalil, Wu, Tianpin, Lu, Jun, & Shahbazian-Yassr, Reza. Dynamic study of (De)sodiation in alpha-MnO2 nanowires. United States. doi:10.1016/j.nanoen.2015.11.028.
Yuan, Yifei, Ma, Lu, He, Kun, Yao, Wentao, Nie, Anmin, Bi, Xuanxuan, Amine, Khalil, Wu, Tianpin, Lu, Jun, and Shahbazian-Yassr, Reza. Fri . "Dynamic study of (De)sodiation in alpha-MnO2 nanowires". United States. doi:10.1016/j.nanoen.2015.11.028.
@article{osti_1247154,
title = {Dynamic study of (De)sodiation in alpha-MnO2 nanowires},
author = {Yuan, Yifei and Ma, Lu and He, Kun and Yao, Wentao and Nie, Anmin and Bi, Xuanxuan and Amine, Khalil and Wu, Tianpin and Lu, Jun and Shahbazian-Yassr, Reza},
abstractNote = {In this report, the electrochemical sodiation and desodiation in single crystalline alpha-MnO2 nanowires are studied dynamically at both single particle level using in situ transmission electron microscopy (TEM) and bulk level using in situ synchrotron X-ray. The TEM results suggest that the first sodiation process starts with tunnel-based Na+ intercalation, experiences the formation of Na0.5MnO2 as a result of tunnel degradation, and ends with the Mn2O3 phase. The inserted Na+ can be partially extracted out of the sodiated products, and the following cycles are dominated by the reversible conversion reaction between Na0.5MnO2 and Mn2O3. The Mn valence evolution inside a cycling coin using alpha-MnO2 nanowire electrode also exhibits partially reversible characteristic, agreeing well with the in situ TEM analysis. The sodiation is compared with lithiation in the same alpha-MnO2 nanowires. Both Na+ and Li+ interact with the tunneled structure via a similar tunnel -driven intercalation mechanism before Mn4+ is reduced to Mn3.5+. For the following deep insertion, the tunnels survive up. to LiMnO2 (Mn3+) during lithiation, while the sodiation proceeds via a different mechanism that involves obvious phase transition and fast tunnel degradation after Mn's valence is below 3.5+. The difference in charge carrier insertion mechanisms can be ascribed to the strong interaction between the tunnel frame and inserted Na+ possessing a larger ionic size than inserted Li+.},
doi = {10.1016/j.nanoen.2015.11.028},
journal = {Nano Energy},
issn = {2211-2855},
number = C,
volume = 19,
place = {United States},
year = {2016},
month = {1}
}