Experimental and Computational Analysis of the Solvent-Dependent O2/Li+-O2- Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries

David G. Kwabi; Vyacheslav S. Bryantsev; Thomas P. Batcho; Daniil M. Itkis; Carl V. Thompson; Yang Shao-Horn

doi:10.1002/anie.201509143

Experimental and Computational Analysis of the Solvent-Dependent O₂/Li⁺-O₂^- Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries

David G. Kwabi, Vyacheslav S. Bryantsev, Thomas P. Batcho, Daniil M. Itkis, Carl V. Thompson, Yang Shao-Horn

Chemical Separations Group

Research output: Contribution to journal › Article › peer-review

124 Scopus citations

Abstract

Understanding and controlling the kinetics of O₂ reduction in the presence of Li⁺-containing aprotic solvents, to either Li⁺-O₂^- by one-electron reduction or Li₂O₂ by two-electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li-O₂ batteries. Standard potentials of O₂/Li⁺-O₂^- and O₂/O₂^- were experimentally measured and computed using a mixed cluster-continuum model of ion solvation. Increasing combined solvation of Li⁺ and O₂^- was found to lower the coupling of Li⁺-O₂^- and the difference between O₂/Li⁺-O₂^- and O₂/O₂^- potentials. The solvation energy of Li⁺ trended with donor number (DN), and varied greater than that of O₂^- ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li⁺-O₂^- 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.

Original language	English
Pages (from-to)	3129-3134
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	9
DOIs	https://doi.org/10.1002/anie.201509143
State	Published - Feb 24 2016

Keywords

acid-base interactions
lithium
oxygen electrochemistry
solvation
superoxide

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10.1002/anie.201509143

Cite this

Kwabi, D. G., Bryantsev, V. S., Batcho, T. P., Itkis, D. M., Thompson, C. V., & Shao-Horn, Y. (2016). Experimental and Computational Analysis of the Solvent-Dependent O₂/Li⁺-O₂^- Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries. Angewandte Chemie - International Edition, 55(9), 3129-3134. https://doi.org/10.1002/anie.201509143

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title = "Experimental and Computational Analysis of the Solvent-Dependent O2/Li+-O2- Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries",

abstract = "Understanding and controlling the kinetics of O2 reduction in the presence of Li+-containing aprotic solvents, to either Li+-O2- by one-electron reduction or Li2O2 by two-electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li-O2 batteries. Standard potentials of O2/Li+-O2- and O2/O2- were experimentally measured and computed using a mixed cluster-continuum model of ion solvation. Increasing combined solvation of Li+ and O2- was found to lower the coupling of Li+-O2- and the difference between O2/Li+-O2- and O2/O2- potentials. The solvation energy of Li+ trended with donor number (DN), and varied greater than that of O2- ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li+-O2- 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.",

keywords = "acid-base interactions, lithium, oxygen electrochemistry, solvation, superoxide",

author = "Kwabi, {David G.} and Bryantsev, {Vyacheslav S.} and Batcho, {Thomas P.} and Itkis, {Daniil M.} and Thompson, {Carl V.} and Yang Shao-Horn",

note = "Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2016",

month = feb,

day = "24",

doi = "10.1002/anie.201509143",

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Kwabi, DG, Bryantsev, VS, Batcho, TP, Itkis, DM, Thompson, CV & Shao-Horn, Y 2016, 'Experimental and Computational Analysis of the Solvent-Dependent O₂/Li⁺-O₂^- Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries', Angewandte Chemie - International Edition, vol. 55, no. 9, pp. 3129-3134. https://doi.org/10.1002/anie.201509143

Experimental and Computational Analysis of the Solvent-Dependent O₂/Li⁺-O₂^- Redox Couple: Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries. / Kwabi, David G.; Bryantsev, Vyacheslav S.; Batcho, Thomas P. et al.
In: Angewandte Chemie - International Edition, Vol. 55, No. 9, 24.02.2016, p. 3129-3134.

Research output: Contribution to journal › Article › peer-review

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T1 - Experimental and Computational Analysis of the Solvent-Dependent O2/Li+-O2- Redox Couple

T2 - Standard Potentials, Coupling Strength, and Implications for Lithium-Oxygen Batteries

AU - Kwabi, David G.

AU - Bryantsev, Vyacheslav S.

AU - Batcho, Thomas P.

AU - Itkis, Daniil M.

AU - Thompson, Carl V.

AU - Shao-Horn, Yang

PY - 2016/2/24

Y1 - 2016/2/24

N2 - Understanding and controlling the kinetics of O2 reduction in the presence of Li+-containing aprotic solvents, to either Li+-O2- by one-electron reduction or Li2O2 by two-electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li-O2 batteries. Standard potentials of O2/Li+-O2- and O2/O2- were experimentally measured and computed using a mixed cluster-continuum model of ion solvation. Increasing combined solvation of Li+ and O2- was found to lower the coupling of Li+-O2- and the difference between O2/Li+-O2- and O2/O2- potentials. The solvation energy of Li+ trended with donor number (DN), and varied greater than that of O2- ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li+-O2- 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.

AB - Understanding and controlling the kinetics of O2 reduction in the presence of Li+-containing aprotic solvents, to either Li+-O2- by one-electron reduction or Li2O2 by two-electron reduction, is instrumental to enhance the discharge voltage and capacity of aprotic Li-O2 batteries. Standard potentials of O2/Li+-O2- and O2/O2- were experimentally measured and computed using a mixed cluster-continuum model of ion solvation. Increasing combined solvation of Li+ and O2- was found to lower the coupling of Li+-O2- and the difference between O2/Li+-O2- and O2/O2- potentials. The solvation energy of Li+ trended with donor number (DN), and varied greater than that of O2- ions, which correlated with acceptor number (AN), explaining a previously reported correlation between Li+-O2- 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.

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KW - lithium

KW - oxygen electrochemistry

KW - solvation

KW - superoxide

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