skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The Influence of Hydrocarbon and CO2 on the Reversibility of Li-O2 Chemistry Using In Situ Ambient Pressure X-ray Photoelectron Spectroscopy

Abstract

Identifying fundamental barriers that hinder reversible lithium oxygen (Li O2) redox reaction is essential for developing efficient and long lasting rechargeable Li O2 batteries. Addressing these challenges is being limited by parasitic reactions in the carbon based O2 electrode with aprotic electrolytes. Understanding the mechanisms of these parasitic reactions is hampered by the complexity that multiple and coupled parasitic reactions involving carbon, electrolytes, and Li O2 reaction intermediates/products can occur simultaneously. In this work, we employed solid state cells free of carbon and aprotic electrolytes to probe the influence of surface adventitious hydrocarbons and carbon dioxide (CO2) on the reversibility of the Li O2 redox chemistry using in situ synchrotron based ambient pressure X ray photoelectron spectroscopy. Direct evidence was provided, for the first time, that surface hydrocarbons and CO2 irreversibly react with Li O2 reaction intermediates/ products such as Li2O2 and Li2O, forming carboxylate and carbonate based species, which cannot be removed fully upon recharge. The slower Li2O2 oxidation kinetics was correlated with increasing coverage of surface carbonate/ carboxylate species. Our work critically points out that materials design that mitigates the reactivity between Li O2 reaction products and common impurities in the atmosphere is needed to achieve long cyclemore » life Li O2 batteries.« less

Authors:
 [1];  [1];  [2];  [2];  [2];  [2];  [3];  [1]
  1. Massachusetts Institute of Technology (MIT)
  2. ORNL
  3. Lawrence Berkeley National Laboratory (LBNL)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1115373
DOE Contract Number:  
DE-AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry C
Additional Journal Information:
Journal Volume: 117; Journal Issue: 49; Journal ID: ISSN 1932--7447
Country of Publication:
United States
Language:
English

Citation Formats

Lu, Yi-chun, Crumlin, Ethan, Carney, Thomas J, Baggetto, Loic, Veith, Gabriel M, Dudney, Nancy J, Liu, Zhi, and Shao-Horn, Yang. The Influence of Hydrocarbon and CO2 on the Reversibility of Li-O2 Chemistry Using In Situ Ambient Pressure X-ray Photoelectron Spectroscopy. United States: N. p., 2013. Web. doi:10.1021/jp409453s.
Lu, Yi-chun, Crumlin, Ethan, Carney, Thomas J, Baggetto, Loic, Veith, Gabriel M, Dudney, Nancy J, Liu, Zhi, & Shao-Horn, Yang. The Influence of Hydrocarbon and CO2 on the Reversibility of Li-O2 Chemistry Using In Situ Ambient Pressure X-ray Photoelectron Spectroscopy. United States. https://doi.org/10.1021/jp409453s
Lu, Yi-chun, Crumlin, Ethan, Carney, Thomas J, Baggetto, Loic, Veith, Gabriel M, Dudney, Nancy J, Liu, Zhi, and Shao-Horn, Yang. Tue . "The Influence of Hydrocarbon and CO2 on the Reversibility of Li-O2 Chemistry Using In Situ Ambient Pressure X-ray Photoelectron Spectroscopy". United States. https://doi.org/10.1021/jp409453s.
@article{osti_1115373,
title = {The Influence of Hydrocarbon and CO2 on the Reversibility of Li-O2 Chemistry Using In Situ Ambient Pressure X-ray Photoelectron Spectroscopy},
author = {Lu, Yi-chun and Crumlin, Ethan and Carney, Thomas J and Baggetto, Loic and Veith, Gabriel M and Dudney, Nancy J and Liu, Zhi and Shao-Horn, Yang},
abstractNote = {Identifying fundamental barriers that hinder reversible lithium oxygen (Li O2) redox reaction is essential for developing efficient and long lasting rechargeable Li O2 batteries. Addressing these challenges is being limited by parasitic reactions in the carbon based O2 electrode with aprotic electrolytes. Understanding the mechanisms of these parasitic reactions is hampered by the complexity that multiple and coupled parasitic reactions involving carbon, electrolytes, and Li O2 reaction intermediates/products can occur simultaneously. In this work, we employed solid state cells free of carbon and aprotic electrolytes to probe the influence of surface adventitious hydrocarbons and carbon dioxide (CO2) on the reversibility of the Li O2 redox chemistry using in situ synchrotron based ambient pressure X ray photoelectron spectroscopy. Direct evidence was provided, for the first time, that surface hydrocarbons and CO2 irreversibly react with Li O2 reaction intermediates/ products such as Li2O2 and Li2O, forming carboxylate and carbonate based species, which cannot be removed fully upon recharge. The slower Li2O2 oxidation kinetics was correlated with increasing coverage of surface carbonate/ carboxylate species. Our work critically points out that materials design that mitigates the reactivity between Li O2 reaction products and common impurities in the atmosphere is needed to achieve long cycle life Li O2 batteries.},
doi = {10.1021/jp409453s},
url = {https://www.osti.gov/biblio/1115373}, journal = {Journal of Physical Chemistry C},
issn = {1932--7447},
number = 49,
volume = 117,
place = {United States},
year = {2013},
month = {1}
}