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Title: Correlating Local Structure with Electrochemical Activity in Li2MnO3

Abstract

Li2MnO3 is of interest as one component of the composite lithium-rich oxides, which are under development for high capacity, high voltage cathodes in lithium ion batteries. Despite such practical importance, the mechanism of electrochemical activity in Li2MnO3 is contested in the literature, as are the effects of long-term electrochemical cycling. Here, Raman spectroscopy and mapping are used to follow the chemical and structural changes that occur in Li2MnO3. Both conventional slurry electrodes and thin films are studied as a function of the state of charge (voltage) and cycle number. Thin films have similar electrochemical properties as electrodes prepared from slurries, but allow for spectroscopic investigations on uniform samples without carbon additives. Spectral changes correlate well with electrochemical activity and support a mechanism whereby capacity is lost upon extended cycling due to the formation of new manganese oxide phases. Raman mapping of both thin film and slurry electrodes charged to different voltages reveals significant variation in the local structure. Poor conductivity and slow kinetics associated with a two-phase reaction mechanism contribute to the heterogeneity.

Authors:
 [1];  [2];  [2];  [2];  [2];  [1];  [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1210144
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 32; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

Nanda, Jagjit, Sacci, Robert L., Veith, Gabriel M., Dixit, Hemant M., Cooper, Valentino R., Pezeshki, Alan M., and Ruther, Rose E. Correlating Local Structure with Electrochemical Activity in Li2MnO3. United States: N. p., 2015. Web. doi:10.1021/acs.jpcc.5b03900.
Nanda, Jagjit, Sacci, Robert L., Veith, Gabriel M., Dixit, Hemant M., Cooper, Valentino R., Pezeshki, Alan M., & Ruther, Rose E. Correlating Local Structure with Electrochemical Activity in Li2MnO3. United States. https://doi.org/10.1021/acs.jpcc.5b03900
Nanda, Jagjit, Sacci, Robert L., Veith, Gabriel M., Dixit, Hemant M., Cooper, Valentino R., Pezeshki, Alan M., and Ruther, Rose E. 2015. "Correlating Local Structure with Electrochemical Activity in Li2MnO3". United States. https://doi.org/10.1021/acs.jpcc.5b03900. https://www.osti.gov/servlets/purl/1210144.
@article{osti_1210144,
title = {Correlating Local Structure with Electrochemical Activity in Li2MnO3},
author = {Nanda, Jagjit and Sacci, Robert L. and Veith, Gabriel M. and Dixit, Hemant M. and Cooper, Valentino R. and Pezeshki, Alan M. and Ruther, Rose E.},
abstractNote = {Li2MnO3 is of interest as one component of the composite lithium-rich oxides, which are under development for high capacity, high voltage cathodes in lithium ion batteries. Despite such practical importance, the mechanism of electrochemical activity in Li2MnO3 is contested in the literature, as are the effects of long-term electrochemical cycling. Here, Raman spectroscopy and mapping are used to follow the chemical and structural changes that occur in Li2MnO3. Both conventional slurry electrodes and thin films are studied as a function of the state of charge (voltage) and cycle number. Thin films have similar electrochemical properties as electrodes prepared from slurries, but allow for spectroscopic investigations on uniform samples without carbon additives. Spectral changes correlate well with electrochemical activity and support a mechanism whereby capacity is lost upon extended cycling due to the formation of new manganese oxide phases. Raman mapping of both thin film and slurry electrodes charged to different voltages reveals significant variation in the local structure. Poor conductivity and slow kinetics associated with a two-phase reaction mechanism contribute to the heterogeneity.},
doi = {10.1021/acs.jpcc.5b03900},
url = {https://www.osti.gov/biblio/1210144}, journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 32,
volume = 119,
place = {United States},
year = {Fri Jul 31 00:00:00 EDT 2015},
month = {Fri Jul 31 00:00:00 EDT 2015}
}

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Cited by: 26 works
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Works referencing / citing this record:

Applications of Conventional Vibrational Spectroscopic Methods for Batteries Beyond Li-Ion
journal, March 2018


Direct observation of layered-to-spinel phase transformation in Li 2 MnO 3 and the spinel structure stabilised after the activation process
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