Solvent- A nd Anion-Dependent Li+-O2                             - Coupling Strength and Implications on the Thermodynamics and Kinetics of Li-O2 Batteries

Graham Leverick; Ryoichi Tatara; Shuting Feng; Emily Crabb; Arthur France-Lanord; Michal Tułodziecki; Jeffrey Lopez; Ryan M. Stephens; Jeffrey C. Grossman; Yang Shao-Horn

doi:10.1021/acs.jpcc.9b09968

Solvent- A nd Anion-Dependent Li⁺-O₂ ^- Coupling Strength and Implications on the Thermodynamics and Kinetics of Li-O₂ Batteries

Graham Leverick^*, Ryoichi Tatara, Shuting Feng, Emily Crabb, Arthur France-Lanord, Michal Tułodziecki, Jeffrey Lopez, Ryan M. Stephens, Jeffrey C. Grossman, Yang Shao-Horn

^*Corresponding author for this work

Chemical and Biological Engineering

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

39 Scopus citations

Abstract

Lithium-oxygen (Li-O₂) batteries offer considerably higher gravimetric energy density than commercial Li-ion batteries (up to three times) but suffer from poor power, cycle life, and round-trip efficiency. Tuning the thermodynamics and pathway of the oxygen reduction reaction (ORR) in aprotic electrolytes can be used to enhance the Li-O₂ battery rate and discharge capacity. In this work, we present a systematic study on the role of the solvent and anion on the thermodynamics and kinetics of Li⁺-ORR, from which we propose a unified descriptor for its pathway and kinetics. First, by thoroughly characterizing the solvation environment of Li⁺ ions using Raman spectroscopy, ⁷Li NMR, ionic conductivity, and viscosity measurements, we observe increasing Li⁺-anion interactions with increasing anion DN in low DN solvents such as 1,2-dimethoxyethane and acetonitrile but minimal Li⁺-anion interactions in the higher DN dimethyl sulfoxide. Next, by determining the electrolyte-dependent Li⁺/Li, TBA⁺,O₂/TBA⁺-O₂ ^-, and Li⁺,O₂/Li⁺-O₂ ^- redox potentials versus the solvent-invariant Me₁₀Fc reference potential, we show that stronger combined solvation of Li⁺ and O₂ ^- ions leads to weaker Li⁺-O₂ ^- coupling. Finally, using rotating ring disk electrode measurements, we show that weaker Li⁺-O₂ ^- coupling in electrolytes with strong combined solvation leads to an increased generation of soluble Li⁺-O₂ ^--type species and faster overall kinetics during Li⁺-ORR.

Original language	English (US)
Pages (from-to)	4953-4967
Number of pages	15
Journal	Journal of Physical Chemistry C
Volume	124
Issue number	9
DOIs	https://doi.org/10.1021/acs.jpcc.9b09968
State	Published - Mar 5 2020

Funding

This work was supported by Shell. This research used resources of the National Energy Research Scientific Computing Center, a DOE office of Science User Facility Supported by the Office of Science of the U.S. Department of Energy under contract no. DE-AC02-5CH11231, and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation grant number ACI-1548562. G.L. was partially supported by a Natural Sciences and Engineering Research Council of Canada (NSERC) PGS-D. S.F. gratefully acknowledges the Link Foundation for an Energy Fellowship. E.C. acknowledges support from the United States Department of Energy through the Computational Sciences Graduate Fellowship (DOE CSGF) under grant number: DE-FG02-97ER25308. J.L. acknowledges support by an appointment to the Intelligence Community Postdoctoral Research Fellowship Program at the Massachusetts Institute of Technology, administered by Oak Ridge Institute for Science and Education through an interagency agreement between the U.S. Department of Energy and the Office of the Director of National Intelligence. We would like to thank Janet Nienhuis for experimental assistance. We would also like to thank David Kwabi for the seminal work in our lab that inspired the ideas conveyed in this manuscript.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acs.jpcc.9b09968

Cite this

Leverick, G., Tatara, R., Feng, S., Crabb, E., France-Lanord, A., Tułodziecki, M., Lopez, J., Stephens, R. M., Grossman, J. C., & Shao-Horn, Y. (2020). Solvent- A nd Anion-Dependent Li⁺-O₂ ^- Coupling Strength and Implications on the Thermodynamics and Kinetics of Li-O₂ Batteries. Journal of Physical Chemistry C, 124(9), 4953-4967. https://doi.org/10.1021/acs.jpcc.9b09968

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title = "Solvent- A nd Anion-Dependent Li+-O2 - Coupling Strength and Implications on the Thermodynamics and Kinetics of Li-O2 Batteries",

abstract = "Lithium-oxygen (Li-O2) batteries offer considerably higher gravimetric energy density than commercial Li-ion batteries (up to three times) but suffer from poor power, cycle life, and round-trip efficiency. Tuning the thermodynamics and pathway of the oxygen reduction reaction (ORR) in aprotic electrolytes can be used to enhance the Li-O2 battery rate and discharge capacity. In this work, we present a systematic study on the role of the solvent and anion on the thermodynamics and kinetics of Li+-ORR, from which we propose a unified descriptor for its pathway and kinetics. First, by thoroughly characterizing the solvation environment of Li+ ions using Raman spectroscopy, 7Li NMR, ionic conductivity, and viscosity measurements, we observe increasing Li+-anion interactions with increasing anion DN in low DN solvents such as 1,2-dimethoxyethane and acetonitrile but minimal Li+-anion interactions in the higher DN dimethyl sulfoxide. Next, by determining the electrolyte-dependent Li+/Li, TBA+,O2/TBA+-O2 -, and Li+,O2/Li+-O2 - redox potentials versus the solvent-invariant Me10Fc reference potential, we show that stronger combined solvation of Li+ and O2 - ions leads to weaker Li+-O2 - coupling. Finally, using rotating ring disk electrode measurements, we show that weaker Li+-O2 - coupling in electrolytes with strong combined solvation leads to an increased generation of soluble Li+-O2 --type species and faster overall kinetics during Li+-ORR.",

author = "Graham Leverick and Ryoichi Tatara and Shuting Feng and Emily Crabb and Arthur France-Lanord and Michal Tu{\l}odziecki and Jeffrey Lopez and Stephens, {Ryan M.} and Grossman, {Jeffrey C.} and Yang Shao-Horn",

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doi = "10.1021/acs.jpcc.9b09968",

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Leverick, G, Tatara, R, Feng, S, Crabb, E, France-Lanord, A, Tułodziecki, M, Lopez, J, Stephens, RM, Grossman, JC & Shao-Horn, Y 2020, 'Solvent- A nd Anion-Dependent Li⁺-O₂ ^- Coupling Strength and Implications on the Thermodynamics and Kinetics of Li-O₂ Batteries', Journal of Physical Chemistry C, vol. 124, no. 9, pp. 4953-4967. https://doi.org/10.1021/acs.jpcc.9b09968

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AU - Leverick, Graham

AU - Tatara, Ryoichi

AU - Feng, Shuting

AU - Crabb, Emily

AU - France-Lanord, Arthur

AU - Tułodziecki, Michal

AU - Lopez, Jeffrey

AU - Stephens, Ryan M.

AU - Grossman, Jeffrey C.

AU - Shao-Horn, Yang

PY - 2020/3/5

Y1 - 2020/3/5

N2 - Lithium-oxygen (Li-O2) batteries offer considerably higher gravimetric energy density than commercial Li-ion batteries (up to three times) but suffer from poor power, cycle life, and round-trip efficiency. Tuning the thermodynamics and pathway of the oxygen reduction reaction (ORR) in aprotic electrolytes can be used to enhance the Li-O2 battery rate and discharge capacity. In this work, we present a systematic study on the role of the solvent and anion on the thermodynamics and kinetics of Li+-ORR, from which we propose a unified descriptor for its pathway and kinetics. First, by thoroughly characterizing the solvation environment of Li+ ions using Raman spectroscopy, 7Li NMR, ionic conductivity, and viscosity measurements, we observe increasing Li+-anion interactions with increasing anion DN in low DN solvents such as 1,2-dimethoxyethane and acetonitrile but minimal Li+-anion interactions in the higher DN dimethyl sulfoxide. Next, by determining the electrolyte-dependent Li+/Li, TBA+,O2/TBA+-O2 -, and Li+,O2/Li+-O2 - redox potentials versus the solvent-invariant Me10Fc reference potential, we show that stronger combined solvation of Li+ and O2 - ions leads to weaker Li+-O2 - coupling. Finally, using rotating ring disk electrode measurements, we show that weaker Li+-O2 - coupling in electrolytes with strong combined solvation leads to an increased generation of soluble Li+-O2 --type species and faster overall kinetics during Li+-ORR.

AB - Lithium-oxygen (Li-O2) batteries offer considerably higher gravimetric energy density than commercial Li-ion batteries (up to three times) but suffer from poor power, cycle life, and round-trip efficiency. Tuning the thermodynamics and pathway of the oxygen reduction reaction (ORR) in aprotic electrolytes can be used to enhance the Li-O2 battery rate and discharge capacity. In this work, we present a systematic study on the role of the solvent and anion on the thermodynamics and kinetics of Li+-ORR, from which we propose a unified descriptor for its pathway and kinetics. First, by thoroughly characterizing the solvation environment of Li+ ions using Raman spectroscopy, 7Li NMR, ionic conductivity, and viscosity measurements, we observe increasing Li+-anion interactions with increasing anion DN in low DN solvents such as 1,2-dimethoxyethane and acetonitrile but minimal Li+-anion interactions in the higher DN dimethyl sulfoxide. Next, by determining the electrolyte-dependent Li+/Li, TBA+,O2/TBA+-O2 -, and Li+,O2/Li+-O2 - redox potentials versus the solvent-invariant Me10Fc reference potential, we show that stronger combined solvation of Li+ and O2 - ions leads to weaker Li+-O2 - coupling. Finally, using rotating ring disk electrode measurements, we show that weaker Li+-O2 - coupling in electrolytes with strong combined solvation leads to an increased generation of soluble Li+-O2 --type species and faster overall kinetics during Li+-ORR.

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