Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via 17O NMR and DFT Calculations
Abstract
Experimental techniques that probe the local environment around O in paramagnetic Li-ion cathode materials are essential in order to understand the complex phase transformations and O redox processes that can occur during electrochemical delithiation. While Li NMR is a well-established technique for studying the local environment of Li ions in paramagnetic battery materials, the use of 17O NMR in the same materials has not yet been reported. In the work reported here, we present a combined 17O NMR and hybrid density functional theory study of the local O environments in Li2MnO3, a model compound for layered Li-ion batteries. After a simple 17O enrichment procedure, we observed five resonances with large 17O shifts ascribed to the Fermi contact interaction with directly bonded Mn4+ ions. The five peaks were separated into two groups with shifts at 1600 to 1950 ppm and 2100 to 2450 ppm, which, with the aid of first-principles calculations, were assigned to the 17O shifts of environments similar to the 4i and 8j sites in pristine Li2MnO3, respectively. The multiple O environments in each region were ascribed to the presence of stacking faults within the Li2MnO3 structure. From the ratio of the intensities of the different 17O environments, themore »
- Authors:
-
- Univ. of Cambridge (United Kingdom)
- Univ. of Warwick, Coventry (United Kingdom)
- Univ. of Cambridge (United Kingdom); Stockholm Univ. (Sweden)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES); Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); Engineering and Physical Sciences Research Council (EPSRC); Trinity College Cambridge; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office. Batteries for Advanced Transportation Technologies (BATT) Program
- OSTI Identifier:
- 1387945
- Grant/Contract Number:
- SC0001294; AC02-98CH10886; SC0012583; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 138; Journal Issue: 30; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; energy storage (including batteries and capacitors); defects; charge transport; materials and chemistry by design; synthesis (novel materials); chemical structure; defects in solids; transition metals; layers; materials
Citation Formats
Seymour, Ieuan D., Middlemiss, Derek S., Halat, David M., Trease, Nicole M., Pell, Andrew J., and Grey, Clare P. Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via 17O NMR and DFT Calculations. United States: N. p., 2016.
Web. doi:10.1021/jacs.6b05747.
Seymour, Ieuan D., Middlemiss, Derek S., Halat, David M., Trease, Nicole M., Pell, Andrew J., & Grey, Clare P. Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via 17O NMR and DFT Calculations. United States. https://doi.org/10.1021/jacs.6b05747
Seymour, Ieuan D., Middlemiss, Derek S., Halat, David M., Trease, Nicole M., Pell, Andrew J., and Grey, Clare P. Tue .
"Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via 17O NMR and DFT Calculations". United States. https://doi.org/10.1021/jacs.6b05747. https://www.osti.gov/servlets/purl/1387945.
@article{osti_1387945,
title = {Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via 17O NMR and DFT Calculations},
author = {Seymour, Ieuan D. and Middlemiss, Derek S. and Halat, David M. and Trease, Nicole M. and Pell, Andrew J. and Grey, Clare P.},
abstractNote = {Experimental techniques that probe the local environment around O in paramagnetic Li-ion cathode materials are essential in order to understand the complex phase transformations and O redox processes that can occur during electrochemical delithiation. While Li NMR is a well-established technique for studying the local environment of Li ions in paramagnetic battery materials, the use of 17O NMR in the same materials has not yet been reported. In the work reported here, we present a combined 17O NMR and hybrid density functional theory study of the local O environments in Li2MnO3, a model compound for layered Li-ion batteries. After a simple 17O enrichment procedure, we observed five resonances with large 17O shifts ascribed to the Fermi contact interaction with directly bonded Mn4+ ions. The five peaks were separated into two groups with shifts at 1600 to 1950 ppm and 2100 to 2450 ppm, which, with the aid of first-principles calculations, were assigned to the 17O shifts of environments similar to the 4i and 8j sites in pristine Li2MnO3, respectively. The multiple O environments in each region were ascribed to the presence of stacking faults within the Li2MnO3 structure. From the ratio of the intensities of the different 17O environments, the percentage of stacking faults was found to be ca. 10%. The methodology for studying 17O shifts in paramagnetic solids described in this work will be useful for studying the local environments of O in a range of technologically interesting transition metal oxides.},
doi = {10.1021/jacs.6b05747},
journal = {Journal of the American Chemical Society},
number = 30,
volume = 138,
place = {United States},
year = {Tue Jul 12 00:00:00 EDT 2016},
month = {Tue Jul 12 00:00:00 EDT 2016}
}
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