Correlating Local Structure with Electrochemical Activity in Li2MnO3

Nanda, Jagjit; Sacci, Robert L.; Veith, Gabriel M.; Dixit, Hemant M.; Cooper, Valentino R.; Pezeshki, Alan M.; Ruther, Rose E.

doi:10.1021/acs.jpcc.5b03900

Title: Correlating Local Structure with Electrochemical Activity in L_i2MnO₃

Journal Article · Fri Jul 31 00:00:00 EDT 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b03900· OSTI ID:1210144

Nanda, Jagjit ^[1]; Sacci, Robert L. ^[2]; Veith, Gabriel M. ^[2]; Dixit, Hemant M. ^[2]; Cooper, Valentino R. ^[2]; Pezeshki, Alan M. ^[1]; Ruther, Rose E. ^[2]

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
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division

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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1210144

Journal Information:: Journal of Physical Chemistry. C, Vol. 119, Issue 32; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 26 works

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Title: Correlating Local Structure with Electrochemical Activity in L_i2MnO₃