In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions
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 p...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | en_US |
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Nature Publishing Group
2013
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| Online Access: | http://hdl.handle.net/1721.1/79102 https://orcid.org/0000-0002-5732-663X |
| _version_ | 1811088246036234240 |
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| author | Lu, Yi-chun Crumlin, Ethan J. Veith, Gabriel M. Harding, Jonathon R. Mutoro, Eva Baggetto, Loic Dudney, Nancy J. Liu, Zhi Shao-Horn, Yang |
| author2 | Massachusetts Institute of Technology. Department of Materials Science and Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Materials Science and Engineering Lu, Yi-chun Crumlin, Ethan J. Veith, Gabriel M. Harding, Jonathon R. Mutoro, Eva Baggetto, Loic Dudney, Nancy J. Liu, Zhi Shao-Horn, Yang |
| author_sort | Lu, Yi-chun |
| collection | MIT |
| description | 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 at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, lithium intercalated into LixV2O5 while molecular oxygen was reduced to form lithium peroxide on LixV2O5 in the presence of oxygen upon discharge. Interestingly, the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of conventional Li-O2 cells with aprotic electrolytes (~1000 mV). Our study provides the 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. |
| first_indexed | 2024-09-23T13:59:01Z |
| format | Article |
| id | mit-1721.1/79102 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:59:01Z |
| publishDate | 2013 |
| publisher | Nature Publishing Group |
| record_format | dspace |
| spelling | mit-1721.1/791022022-10-01T18:20:19Z In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions Lu, Yi-chun Crumlin, Ethan J. Veith, Gabriel M. Harding, Jonathon R. Mutoro, Eva Baggetto, Loic Dudney, Nancy J. Liu, Zhi Shao-Horn, Yang Massachusetts Institute of Technology. Department of Materials Science and Engineering Massachusetts Institute of Technology. Department of Mechanical Engineering Massachusetts Institute of Technology. Electrochemical Energy Laboratory Lu, Yi-chun Crumlin, Ethan J. Veith, Gabriel M. Mutoro, Eva Shao-Horn, Yang 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 at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, lithium intercalated into LixV2O5 while molecular oxygen was reduced to form lithium peroxide on LixV2O5 in the presence of oxygen upon discharge. Interestingly, the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of conventional Li-O2 cells with aprotic electrolytes (~1000 mV). Our study provides the 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. National Science Foundation (U.S.) (Materials Research Science and Engineering Center (MRSEC) Program, Award DMR-0819762) United States. Dept. of Energy (Assistant Secretary for Energy Efficiency and Renewable Energy, Office of FreedomCAR and Vehicle Technologies of the U. S. Department of Energy under contract no. DE-AC03-76SF00098) Lawrence Berkeley National Laboratory United States. Dept. of Energy (Office of Basic Energy Sciences, Materials Sciences and Engineering) 2013-06-13T20:11:39Z 2013-06-13T20:11:39Z 2012-10 2012-07 Article http://purl.org/eprint/type/JournalArticle 2045-2322 http://hdl.handle.net/1721.1/79102 Lu, Yi-Chun, Ethan J. Crumlin, Gabriel M. Veith, Jonathon R. Harding, Eva Mutoro, Loïc Baggetto, Nancy J. Dudney, Zhi Liu, and Yang Shao-Horn. In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions. Scientific Reports 2 (October 8, 2012). https://orcid.org/0000-0002-5732-663X en_US http://dx.doi.org/10.1038/srep00715 Scientific Reports Creative Commons Attribution-Noncommercial-Share Alike 3.0 http://creativecommons.org/licenses/by-nc-sa/3.0/ application/pdf Nature Publishing Group Scientific Reports |
| spellingShingle | Lu, Yi-chun Crumlin, Ethan J. Veith, Gabriel M. Harding, Jonathon R. Mutoro, Eva Baggetto, Loic Dudney, Nancy J. Liu, Zhi Shao-Horn, Yang In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions |
| title | In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions |
| title_full | In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions |
| title_fullStr | In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions |
| title_full_unstemmed | In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions |
| title_short | In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions |
| title_sort | in situ ambient pressure x ray photoelectron spectroscopy studies of lithium oxygen redox reactions |
| url | http://hdl.handle.net/1721.1/79102 https://orcid.org/0000-0002-5732-663X |
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