Adiabatic and Nonadiabatic Charge Transport in Li-S Batteries

Haesun Park, Nitin Kumar, Marko Melander, Tejs Vegge, Juan Maria García Lastra, Donald Jason Siegel*

*Corresponding author for this work

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Abstract

The insulating nature of the redox end members in Li-S batteries, -S and Li2S, has the potential to limit the capacity and efficiency of this emerging energy storage system. Nevertheless, the mechanisms responsible for ionic and electronic transport in these materials remain a matter of debate. The present study clarifies these mechanisms – in both the adiabatic and nonadiabatic charge transfer regimes – by employing a combination of hybrid-functional-based and constrained density functional theory calculations. Charge transfer in Li2S is predicted to be adiabatic, and thus is well described by conventional DFT methodologies. In sulfur, however, transitions between S8 rings are nonadiabatic. In this case, conventional DFT overestimates charge transfer rates by up to 2 orders of magnitude. Delocalized holes, and to a lesser extent, localized electron polarons, are predicted to be the most mobile electronic charge carriers in -S; in Li2S hole polarons dominate. Although all carriers exhibit extremely low equilibrium concentrations, and thus yield negligible contributions to the conductivity, their mobilities are sufficient to enable the sulfur loading targets necessary for high energy densities. Our results highlight the value of methods capable of capturing nonadiabadicty, such as constrained DFT. These techniques are especially important for molecular crystals such as -S, where longer-range charge transfer events are expected. Combining the present computational results with prior experimental studies, we conclude that low equilibrium carrier concentrations are responsible for sluggish charge transport in -S and Li2S. Thus, a potential strategy for improving the performance of Li-S batteries is to increase the concentrations of holes in these redox end members.
Original languageEnglish
JournalChemistry of Materials
Volume30
Issue number3
Pages (from-to)915-928
ISSN0897-4756
DOIs
Publication statusPublished - 2018

Cite this

Park, Haesun ; Kumar, Nitin ; Melander, Marko ; Vegge, Tejs ; García Lastra, Juan Maria ; Siegel, Donald Jason. / Adiabatic and Nonadiabatic Charge Transport in Li-S Batteries. In: Chemistry of Materials. 2018 ; Vol. 30, No. 3. pp. 915-928.
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title = "Adiabatic and Nonadiabatic Charge Transport in Li-S Batteries",
abstract = "The insulating nature of the redox end members in Li-S batteries, -S and Li2S, has the potential to limit the capacity and efficiency of this emerging energy storage system. Nevertheless, the mechanisms responsible for ionic and electronic transport in these materials remain a matter of debate. The present study clarifies these mechanisms – in both the adiabatic and nonadiabatic charge transfer regimes – by employing a combination of hybrid-functional-based and constrained density functional theory calculations. Charge transfer in Li2S is predicted to be adiabatic, and thus is well described by conventional DFT methodologies. In sulfur, however, transitions between S8 rings are nonadiabatic. In this case, conventional DFT overestimates charge transfer rates by up to 2 orders of magnitude. Delocalized holes, and to a lesser extent, localized electron polarons, are predicted to be the most mobile electronic charge carriers in -S; in Li2S hole polarons dominate. Although all carriers exhibit extremely low equilibrium concentrations, and thus yield negligible contributions to the conductivity, their mobilities are sufficient to enable the sulfur loading targets necessary for high energy densities. Our results highlight the value of methods capable of capturing nonadiabadicty, such as constrained DFT. These techniques are especially important for molecular crystals such as -S, where longer-range charge transfer events are expected. Combining the present computational results with prior experimental studies, we conclude that low equilibrium carrier concentrations are responsible for sluggish charge transport in -S and Li2S. Thus, a potential strategy for improving the performance of Li-S batteries is to increase the concentrations of holes in these redox end members.",
author = "Haesun Park and Nitin Kumar and Marko Melander and Tejs Vegge and {Garc{\'i}a Lastra}, {Juan Maria} and Siegel, {Donald Jason}",
year = "2018",
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Adiabatic and Nonadiabatic Charge Transport in Li-S Batteries. / Park, Haesun ; Kumar, Nitin; Melander, Marko; Vegge, Tejs; García Lastra, Juan Maria; Siegel, Donald Jason.

In: Chemistry of Materials, Vol. 30, No. 3, 2018, p. 915-928.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - Adiabatic and Nonadiabatic Charge Transport in Li-S Batteries

AU - Park, Haesun

AU - Kumar, Nitin

AU - Melander, Marko

AU - Vegge, Tejs

AU - García Lastra, Juan Maria

AU - Siegel, Donald Jason

PY - 2018

Y1 - 2018

N2 - The insulating nature of the redox end members in Li-S batteries, -S and Li2S, has the potential to limit the capacity and efficiency of this emerging energy storage system. Nevertheless, the mechanisms responsible for ionic and electronic transport in these materials remain a matter of debate. The present study clarifies these mechanisms – in both the adiabatic and nonadiabatic charge transfer regimes – by employing a combination of hybrid-functional-based and constrained density functional theory calculations. Charge transfer in Li2S is predicted to be adiabatic, and thus is well described by conventional DFT methodologies. In sulfur, however, transitions between S8 rings are nonadiabatic. In this case, conventional DFT overestimates charge transfer rates by up to 2 orders of magnitude. Delocalized holes, and to a lesser extent, localized electron polarons, are predicted to be the most mobile electronic charge carriers in -S; in Li2S hole polarons dominate. Although all carriers exhibit extremely low equilibrium concentrations, and thus yield negligible contributions to the conductivity, their mobilities are sufficient to enable the sulfur loading targets necessary for high energy densities. Our results highlight the value of methods capable of capturing nonadiabadicty, such as constrained DFT. These techniques are especially important for molecular crystals such as -S, where longer-range charge transfer events are expected. Combining the present computational results with prior experimental studies, we conclude that low equilibrium carrier concentrations are responsible for sluggish charge transport in -S and Li2S. Thus, a potential strategy for improving the performance of Li-S batteries is to increase the concentrations of holes in these redox end members.

AB - The insulating nature of the redox end members in Li-S batteries, -S and Li2S, has the potential to limit the capacity and efficiency of this emerging energy storage system. Nevertheless, the mechanisms responsible for ionic and electronic transport in these materials remain a matter of debate. The present study clarifies these mechanisms – in both the adiabatic and nonadiabatic charge transfer regimes – by employing a combination of hybrid-functional-based and constrained density functional theory calculations. Charge transfer in Li2S is predicted to be adiabatic, and thus is well described by conventional DFT methodologies. In sulfur, however, transitions between S8 rings are nonadiabatic. In this case, conventional DFT overestimates charge transfer rates by up to 2 orders of magnitude. Delocalized holes, and to a lesser extent, localized electron polarons, are predicted to be the most mobile electronic charge carriers in -S; in Li2S hole polarons dominate. Although all carriers exhibit extremely low equilibrium concentrations, and thus yield negligible contributions to the conductivity, their mobilities are sufficient to enable the sulfur loading targets necessary for high energy densities. Our results highlight the value of methods capable of capturing nonadiabadicty, such as constrained DFT. These techniques are especially important for molecular crystals such as -S, where longer-range charge transfer events are expected. Combining the present computational results with prior experimental studies, we conclude that low equilibrium carrier concentrations are responsible for sluggish charge transport in -S and Li2S. Thus, a potential strategy for improving the performance of Li-S batteries is to increase the concentrations of holes in these redox end members.

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JF - Chemistry of Materials

SN - 0897-4756

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