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Title: Reaction Mechanisms for the Limited Reversibility of Li-O2 Chemistry in Organic Carbonate Electrolytes

Abstract

The Li-O2 chemistry in nonaqueous carbonate electrolytes and the underneath reason of its limited reversibility was exhaustively investigated. The discharge products collected from the air cathode in a Li-O2 battery at different depth of discharge (DOD) were systematically analyzed with X-ray diffraction. It is revealed that, independent of the discharge depth, lithium alkylcarbonate (either lithium propylenedicarbonate - LPDC, or lithium ethylenedicarbonate - LEDC, with other related derivatives) and lithium carbonate (Li2CO3) are always the main products, obviously originated from the electrolyte solvents propylene carbonate (PC) and ethylene carbonate (EC). These lithium alkylcarbonates are obviously generated from the single-electron reductive decomposition of the corresponding carbonate solvents initiated by the attack of superoxide radical anions. On the other hand, neither lithium peroxide (Li2O2) nor lithium oxide (Li2O) is detected. More significantly, from in situ gas chromatography/mass spectroscopy it is found that Li2CO3 and Li2O cannot be oxidized even when charged up to 4.6 V vs. Li/Li+, while LPDC, LEDC and Li2O2 are readily able to, with CO2 and CO released with the re-oxidation of LPDC and LEDC. It is therefore concluded that the quasi-reversibility of Li-O2 chemistry observed hitherto in an organic carbonate-based electrolyte is actually reliant on the formation of lithiummore » alkylcarbonates through the reductive decomposition of carbonate solvents during discharge process and the subsequent oxidation of these same alkylcarbonates during charge process. It is the poor oxidizability of these alkylcarbonate species that constitutes the obstruction to an ideal rechargeable Li-O2 battery.« less

Authors:
; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1027690
Report Number(s):
PNNL-SA-78429
Journal ID: ISSN 0378-7753; JPSODZ; TRN: US201121%%527
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Power Sources
Additional Journal Information:
Journal Volume: 196; Journal Issue: 22; Journal ID: ISSN 0378-7753
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AIR; ANIONS; CARBONATES; CARBONIC ACID ESTERS; CATHODES; CHEMISTRY; ELECTROLYTES; ETHYLENE; LITHIUM; LITHIUM CARBONATES; LITHIUM OXIDES; OXIDATION; PEROXIDES; REACTION KINETICS; SOLVENTS; SPECTROSCOPY; SUPEROXIDE RADICALS; X-RAY DIFFRACTION; Li-O2 battery chemistry; Carbonate electrolyte; Reversibility; Cycleability; Lithium alkylcarbonate; Gas chromatography/mass spectroscopy

Citation Formats

Xu, Wu, Xu, Kang, Viswanathan, Vilayanur V, Towne, Silas A, Hardy, John S, Xiao, Jie, Nie, Zimin, Hu, Dehong, Wang, Deyu, and Zhang, Jiguang. Reaction Mechanisms for the Limited Reversibility of Li-O2 Chemistry in Organic Carbonate Electrolytes. United States: N. p., 2011. Web. doi:10.1016/j.jpowsour.2011.06.099.
Xu, Wu, Xu, Kang, Viswanathan, Vilayanur V, Towne, Silas A, Hardy, John S, Xiao, Jie, Nie, Zimin, Hu, Dehong, Wang, Deyu, & Zhang, Jiguang. Reaction Mechanisms for the Limited Reversibility of Li-O2 Chemistry in Organic Carbonate Electrolytes. United States. https://doi.org/10.1016/j.jpowsour.2011.06.099
Xu, Wu, Xu, Kang, Viswanathan, Vilayanur V, Towne, Silas A, Hardy, John S, Xiao, Jie, Nie, Zimin, Hu, Dehong, Wang, Deyu, and Zhang, Jiguang. Tue . "Reaction Mechanisms for the Limited Reversibility of Li-O2 Chemistry in Organic Carbonate Electrolytes". United States. https://doi.org/10.1016/j.jpowsour.2011.06.099.
@article{osti_1027690,
title = {Reaction Mechanisms for the Limited Reversibility of Li-O2 Chemistry in Organic Carbonate Electrolytes},
author = {Xu, Wu and Xu, Kang and Viswanathan, Vilayanur V and Towne, Silas A and Hardy, John S and Xiao, Jie and Nie, Zimin and Hu, Dehong and Wang, Deyu and Zhang, Jiguang},
abstractNote = {The Li-O2 chemistry in nonaqueous carbonate electrolytes and the underneath reason of its limited reversibility was exhaustively investigated. The discharge products collected from the air cathode in a Li-O2 battery at different depth of discharge (DOD) were systematically analyzed with X-ray diffraction. It is revealed that, independent of the discharge depth, lithium alkylcarbonate (either lithium propylenedicarbonate - LPDC, or lithium ethylenedicarbonate - LEDC, with other related derivatives) and lithium carbonate (Li2CO3) are always the main products, obviously originated from the electrolyte solvents propylene carbonate (PC) and ethylene carbonate (EC). These lithium alkylcarbonates are obviously generated from the single-electron reductive decomposition of the corresponding carbonate solvents initiated by the attack of superoxide radical anions. On the other hand, neither lithium peroxide (Li2O2) nor lithium oxide (Li2O) is detected. More significantly, from in situ gas chromatography/mass spectroscopy it is found that Li2CO3 and Li2O cannot be oxidized even when charged up to 4.6 V vs. Li/Li+, while LPDC, LEDC and Li2O2 are readily able to, with CO2 and CO released with the re-oxidation of LPDC and LEDC. It is therefore concluded that the quasi-reversibility of Li-O2 chemistry observed hitherto in an organic carbonate-based electrolyte is actually reliant on the formation of lithium alkylcarbonates through the reductive decomposition of carbonate solvents during discharge process and the subsequent oxidation of these same alkylcarbonates during charge process. It is the poor oxidizability of these alkylcarbonate species that constitutes the obstruction to an ideal rechargeable Li-O2 battery.},
doi = {10.1016/j.jpowsour.2011.06.099},
url = {https://www.osti.gov/biblio/1027690}, journal = {Journal of Power Sources},
issn = {0378-7753},
number = 22,
volume = 196,
place = {United States},
year = {2011},
month = {11}
}