In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

doi:https://doi.org/10.1038/srep00715

Title: In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

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Abstract

The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and near ambient-pressure of oxygen using X-ray photoelectron spectroscopy (APXPS). Oxygen reduction and evolution reactions take place on the surface of the mixed electronic and Li+ ionic conductor, LixV2O5, which eliminate parasitic reactions between oxygen reduction/evolution reaction intermediates and aprotic electrolytes used in Li-O2 batteries reported to date. Under UHV, reversible lithium intercalation and de-intercalation from LixV2O5 was noted, where the changes in the vanadium valence state revealed from XPS in this study were comparable to that reported previously from Li/LixV2O5 thin film batteries. In presence of oxygen near ambient pressure, the LixV2O5 surface was covered gradually by the reaction product of oxygen reduction, namely lithium peroxide (Li2O2) (approximately 1-2 unit cells) upon discharge. Interestingly, the LixV2O5 surface became re-exposed upon charging, and the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of Li-O2 cells (~1000 mV) with aprotic electrolytes, whichmore »« less

Authors:: Lu, Yi-Chun; Crumlin, Ethan J.; Veith, Gabriel M.; Harding, Jonathon R.; Mutoro, Eva; Baggetto, Loïc; Dudney, Nancy J.; Liu, Zhi; Shao-Horn, Yang

Publication Date:: 2012-10-08

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1060837

DOE Contract Number:: DE-AC05-00OR22725

Resource Type:: Journal Article

Journal Name:: Scientific Reports

Additional Journal Information:: Journal Volume: 2; Journal Issue: 715; Journal ID: ISSN 2045-2322

Publisher:: Nature Publishing Group

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Lu, Yi-Chun, Crumlin, Ethan J., Veith, Gabriel M., Harding, Jonathon R., Mutoro, Eva, Baggetto, Loïc, Dudney, Nancy J., Liu, Zhi, and Shao-Horn, Yang. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions.  United States: N. p., 2012. 
        Web.  doi:10.1038/srep00715.

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                    Lu, Yi-Chun, Crumlin, Ethan J., Veith, Gabriel M., Harding, Jonathon R., Mutoro, Eva, Baggetto, Loïc, Dudney, Nancy J., Liu, Zhi, & Shao-Horn, Yang. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions.  United States.  https://doi.org/10.1038/srep00715

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                    Lu, Yi-Chun, Crumlin, Ethan J., Veith, Gabriel M., Harding, Jonathon R., Mutoro, Eva, Baggetto, Loïc, Dudney, Nancy J., Liu, Zhi, and Shao-Horn, Yang. Mon .  
        "In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions".  United States.  https://doi.org/10.1038/srep00715.

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@article{osti_1060837,

  title        = {In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions},

  author       = {Lu, Yi-Chun and Crumlin, Ethan J. and Veith, Gabriel M. and Harding, Jonathon R. and Mutoro, Eva and Baggetto, Loïc and Dudney, Nancy J. and Liu, Zhi and Shao-Horn, Yang},

  abstractNote = {The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and near ambient-pressure of oxygen using X-ray photoelectron spectroscopy (APXPS). Oxygen reduction and evolution reactions take place on the surface of the mixed electronic and Li+ ionic conductor, LixV2O5, which eliminate parasitic reactions between oxygen reduction/evolution reaction intermediates and aprotic electrolytes used in Li-O2 batteries reported to date. Under UHV, reversible lithium intercalation and de-intercalation from LixV2O5 was noted, where the changes in the vanadium valence state revealed from XPS in this study were comparable to that reported previously from Li/LixV2O5 thin film batteries. In presence of oxygen near ambient pressure, the LixV2O5 surface was covered gradually by the reaction product of oxygen reduction, namely lithium peroxide (Li2O2) (approximately 1-2 unit cells) upon discharge. Interestingly, the LixV2O5 surface became re-exposed upon charging, and the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of Li-O2 cells (~1000 mV) with aprotic electrolytes, which can be attributed to subnanometer-thick Li2O2 with surfaces free of contaminants such as carbonate species. Our study provides first evidence of reversible lithium peroxide formation and decomposition in situ on an oxide surface using a solid-state cell, and new insights into the reaction mechanism of Li-O2 chemistry.},

  doi          = {10.1038/srep00715},

  url          = {https://www.osti.gov/biblio/1060837},
  journal      = {Scientific Reports},

  issn         = {2045-2322},

  number       = 715,

  volume       = 2,

  place        = {United States},

  year         = {2012},

  month        = {10}

}

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