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Title: Experimental and Computational Analysis of the Solvent‐Dependent O 2 /Li + ‐O 2 − Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries

Abstract

Abstract Understanding and controlling the kinetics of O 2 reduction in the presence of Li + ‐containing aprotic solvents, to either Li + ‐O 2 − by one‐electron reduction or Li 2 O 2 by two‐electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li‐O 2 batteries. Standard potentials of O 2 /Li + ‐O 2 − and O 2 /O 2 − were experimentally measured and computed using a mixed cluster‐continuum model of ion solvation. Increasing combined solvation of Li + and O 2 − was found to lower the coupling of Li + ‐O 2 − and the difference between O 2 /Li + ‐O 2 − and O 2 /O 2 − potentials. The solvation energy of Li + trended with donor number (DN), and varied greater than that of O 2 − ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li + ‐O 2 − solubility and DN. These results highlight the importance of the interplay between ion–solvent and ion–ion interactions for manipulating the energetics of intermediate species produced in aprotic metal–oxygen batteries.

Authors:
 [1];  [2];  [3];  [4];  [3];  [5]
+ Show Author Affiliations
  1. Department of Mechanical Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA
  2. Liox Power Inc 129 North Hill Ave, Suite 103 Pasadena CA 911106 USA, Oak Ridge National Lab Chemical Sciences Division 1 Bethel Valley Rd Oak Ridge TN 37831-6119 USA
  3. Department of Materials Science and Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA
  4. Department of Chemistry and Materials Science Moscow State University Moscow 119992 Russia
  5. Department of Mechanical Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA, Department of Materials Science and Engineering Massachusetts Institute of Technology 77 Massachusetts Avenue Cambridge MA 02139 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400735
Grant/Contract Number:  
PI0000012
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition) Journal Volume: 55 Journal Issue: 9; Journal ID: ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Kwabi, David G., Bryantsev, Vyacheslav S., Batcho, Thomas P., Itkis, Daniil M., Thompson, Carl V., and Shao‐Horn, Yang. Experimental and Computational Analysis of the Solvent‐Dependent O 2 /Li + ‐O 2 − Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries. Germany: N. p., 2016. Web. doi:10.1002/anie.201509143.
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Kwabi, David G., Bryantsev, Vyacheslav S., Batcho, Thomas P., Itkis, Daniil M., Thompson, Carl V., & Shao‐Horn, Yang. Experimental and Computational Analysis of the Solvent‐Dependent O 2 /Li + ‐O 2 − Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries. Germany. https://doi.org/10.1002/anie.201509143
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Kwabi, David G., Bryantsev, Vyacheslav S., Batcho, Thomas P., Itkis, Daniil M., Thompson, Carl V., and Shao‐Horn, Yang. Thu . "Experimental and Computational Analysis of the Solvent‐Dependent O 2 /Li + ‐O 2 − Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries". Germany. https://doi.org/10.1002/anie.201509143.
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@article{osti_1400735,
title = {Experimental and Computational Analysis of the Solvent‐Dependent O 2 /Li + ‐O 2 − Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium–Oxygen Batteries},
author = {Kwabi, David G. and Bryantsev, Vyacheslav S. and Batcho, Thomas P. and Itkis, Daniil M. and Thompson, Carl V. and Shao‐Horn, Yang},
abstractNote = {Abstract Understanding and controlling the kinetics of O 2 reduction in the presence of Li + ‐containing aprotic solvents, to either Li + ‐O 2 − by one‐electron reduction or Li 2 O 2 by two‐electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li‐O 2 batteries. Standard potentials of O 2 /Li + ‐O 2 − and O 2 /O 2 − were experimentally measured and computed using a mixed cluster‐continuum model of ion solvation. Increasing combined solvation of Li + and O 2 − was found to lower the coupling of Li + ‐O 2 − and the difference between O 2 /Li + ‐O 2 − and O 2 /O 2 − potentials. The solvation energy of Li + trended with donor number (DN), and varied greater than that of O 2 − ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li + ‐O 2 − solubility and DN. These results highlight the importance of the interplay between ion–solvent and ion–ion interactions for manipulating the energetics of intermediate species produced in aprotic metal–oxygen batteries.},
doi = {10.1002/anie.201509143},
journal = {Angewandte Chemie (International Edition)},
number = 9,
volume = 55,
place = {Germany},
year = {Thu Jan 28 00:00:00 EST 2016},
month = {Thu Jan 28 00:00:00 EST 2016}
}
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https://doi.org/10.1002/anie.201509143
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