Adiabatic and Nonadiabatic Charge Transport in Li–S Batteries

Park, Haesun; Kumar, Nitin; Melander, Marko; Vegge, Tejs; Lastra, Juan Maria García; Siegel, Donald J.

doi:10.1021/acs.chemmater.7b04618

Cited by 37 publications

(56 citation statements)

References 99 publications

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“…Based on a nudged elastic band (NEB) analysis, we found that the latter active support from (di)sulfide anions can lower diffusion barrier from 2.16 to 1.50 eV. A more detailed investigation on the dynamic properties of this system, including, for example, the specifics of the electron-transport mechanism [31] and an automated workflow analysis of the Mgkinetics could shed additional light on this interesting process.…”

Section: àmentioning

confidence: 90%

Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

et al. 2020

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The development of multivalent metal (such as Mg and Ca) based battery systems is hindered by lack of suitable cathode chemistry that shows reversible multi‐electron redox reactions. Cationic redox centres in the classical cathodes can only afford stepwise single‐electron transfer, which are not ideal for multivalent‐ion storage. The charge imbalance during multivalent ion insertion might lead to an additional kinetic barrier for ion mobility. Therefore, multivalent battery cathodes only exhibit slope‐like voltage profiles with insertion/extraction redox of less than one electron. Taking VS 4 as a model material, reversible two‐electron redox with cationic–anionic contributions is verified in both rechargeable Mg batteries (RMBs) and rechargeable Ca batteries (RCBs). The corresponding cells exhibit high capacities of >300 mAh g −1 at a current density of 100 mA g −1 in both RMBs and RCBs, resulting in a high energy density of >300 Wh kg −1 for RMBs and >500 Wh kg −1 for RCBs. Mechanistic studies reveal a unique redox activity mainly at anionic sulfides moieties and fast Mg 2+ ion diffusion kinetics enabled by the soft structure and flexible electron configuration of VS 4 .

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Section: àmentioning

confidence: 90%

Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

et al. 2020

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“…Instead, as demonstrated herein, ET, PT, or PCET and bond rupture/formation are naturally captured with GCE-DFT. Bond formation s is also captured by diabatic models using cDFT as demonstrated herein for the Volmer reaction and previously for ET [138], PCET [139] and general chemical reactions [140,141].…”

Section: Discussionmentioning

confidence: 75%

Grand Canonical Rate Theory for Electrochemical and Electrocatalytic Systems I: General Formulation and Proton-coupled Electron Transfer Reactions

Melander

2020

J. Electrochem. Soc.

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A generally valid rate theory at fixed potentials is developed to treat electrochemical and electrocatalytic potential-dependent electron, proton, and proton-coupled electron reactions. Both classical and quantum reactions in adiabatic and non-adiabatic limits are treated. The applicability and new information obtained from the theory is demonstrated for the gold catalyzed acidic Volmer reaction. File list (3) download file view on ChemRxiv appendix.pdf (649.78 KiB) download file view on ChemRxiv main_article.pdf (1.12 MiB) download file view on ChemRxiv supporting_info.pdf (384.50 KiB)

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“…Based on a nudged elastic band (NEB) analysis, we found that the latter active support from (di)sulfide anions can lower diffusion barrier from 2.16 to 1.50 eV. A more detailed investigation on the dynamic properties of this system, including, for example, the specifics of the electron‐transport mechanism [31] and an automated workflow analysis of the Mg‐kinetics could shed additional light on this interesting process.…”

Section: Resultsmentioning

confidence: 91%

Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

Vinayan

Jankowski

et al. 2020

Angewandte Chemie

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The development of multivalent metal (such as Mg and Ca) based battery systems is hindered by lack of suitable cathode chemistry that shows reversible multi‐electron redox reactions. Cationic redox centres in the classical cathodes can only afford stepwise single‐electron transfer, which are not ideal for multivalent‐ion storage. The charge imbalance during multivalent ion insertion might lead to an additional kinetic barrier for ion mobility. Therefore, multivalent battery cathodes only exhibit slope‐like voltage profiles with insertion/extraction redox of less than one electron. Taking VS4 as a model material, reversible two‐electron redox with cationic–anionic contributions is verified in both rechargeable Mg batteries (RMBs) and rechargeable Ca batteries (RCBs). The corresponding cells exhibit high capacities of >300 mAh g−1 at a current density of 100 mA g−1 in both RMBs and RCBs, resulting in a high energy density of >300 Wh kg−1 for RMBs and >500 Wh kg−1 for RCBs. Mechanistic studies reveal a unique redox activity mainly at anionic sulfides moieties and fast Mg2+ ion diffusion kinetics enabled by the soft structure and flexible electron configuration of VS4.

show abstract

Adiabatic and Nonadiabatic Charge Transport in Li–S Batteries

Cited by 37 publications

References 99 publications

Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

Grand Canonical Rate Theory for Electrochemical and Electrocatalytic Systems I: General Formulation and Proton-coupled Electron Transfer Reactions

Multi‐Electron Reactions Enabled by Anion‐Based Redox Chemistry for High‐Energy Multivalent Rechargeable Batteries

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