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Title: Nanostructured metal carbides for aprotic Li-O2 batteries. New insights into interfacial reactions and cathode stability

Abstract

The development of nonaqueous Li–oxygen batteries, which relies on the reversible reaction of Li + O2 to give lithium peroxide (Li2O2), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li2O2 oxidation on a passivated nanostructured metallic carbide (Mo2C), carbon-free cathode host. Furthermore, online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the LixMoO3-passivated conductive interface formed on the carbide, owing to their close redox potentials. We found that the process rejuvenates the surface on each cycle upon electrochemical charge by releasing LixMoO3 into the electrolyte, explaining the low charging potential.

Authors:
 [1];  [1];  [1];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Waterloo, ON (Canada)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1235282
Report Number(s):
SAND-2015-4343J
Journal ID: ISSN 1948-7185; 590459
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 6; Journal Issue: 12; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; lithium-air; oxygen reduction; aprotic medial online mass spectrometry

Citation Formats

Kundu, Dipan, Black, Robert, Adams, Brian, Harrison, Katharine, Zavadil, Kevin R., and Nazar, Linda F. Nanostructured metal carbides for aprotic Li-O2 batteries. New insights into interfacial reactions and cathode stability. United States: N. p., 2015. Web. doi:10.1021/acs.jpclett.5b00721.
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Kundu, Dipan, Black, Robert, Adams, Brian, Harrison, Katharine, Zavadil, Kevin R., & Nazar, Linda F. Nanostructured metal carbides for aprotic Li-O2 batteries. New insights into interfacial reactions and cathode stability. United States. https://doi.org/10.1021/acs.jpclett.5b00721
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Kundu, Dipan, Black, Robert, Adams, Brian, Harrison, Katharine, Zavadil, Kevin R., and Nazar, Linda F. Fri . "Nanostructured metal carbides for aprotic Li-O2 batteries. New insights into interfacial reactions and cathode stability". United States. https://doi.org/10.1021/acs.jpclett.5b00721. https://www.osti.gov/servlets/purl/1235282.
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@article{osti_1235282,
title = {Nanostructured metal carbides for aprotic Li-O2 batteries. New insights into interfacial reactions and cathode stability},
author = {Kundu, Dipan and Black, Robert and Adams, Brian and Harrison, Katharine and Zavadil, Kevin R. and Nazar, Linda F.},
abstractNote = {The development of nonaqueous Li–oxygen batteries, which relies on the reversible reaction of Li + O2 to give lithium peroxide (Li2O2), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li2O2 oxidation on a passivated nanostructured metallic carbide (Mo2C), carbon-free cathode host. Furthermore, online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the LixMoO3-passivated conductive interface formed on the carbide, owing to their close redox potentials. We found that the process rejuvenates the surface on each cycle upon electrochemical charge by releasing LixMoO3 into the electrolyte, explaining the low charging potential.},
doi = {10.1021/acs.jpclett.5b00721},
journal = {Journal of Physical Chemistry Letters},
number = 12,
volume = 6,
place = {United States},
year = {Fri May 01 00:00:00 EDT 2015},
month = {Fri May 01 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acs.jpclett.5b00721
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    Catalysts in metal–air batteries
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