The mechanism of charge transfer between metal ions and graphene in the presence of an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate) is investigated by means of density functional theory calculations. For that purpose, two different comparisons are established: (i) the behavior of Li+ and K+ when adsorbed onto the basal plane of graphene and (ii) the differences between Li+ approaching the carbon surface from the basal plane and being intercalated through the edge plane of trilayer graphene. In the first case, it is found that the metal ions must overcome high energy barriers due to their interaction with the ionic liquid before reaching an equilibrium position close to the interface. In addition, no significant charge transfer between any of the metals and graphene takes place until very close energetically unfavorable distances. The second configuration shows that Li+ has no equilibrium position in the proximity of the interface but instead has an equilibrium position when it is inside the electrode for which it has to cross an energy barrier. In this case, the formation of a LiC12 complex is observed since the charge transfer at the equilibrium distance is achieved to a considerable extent. Thus, the interfacial charge transfer resistance on the electrode in energy devices based on ionic liquids clearly depends not only on the binding of the ionic liquid to the metal cations and their ability to form a dense solvation shell around them but also on the surface topography and its effect on the ion packing on the surface.
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7 January 2022
Research Article|
January 06 2022
Density functional theory of alkali metals at the IL/graphene electrochemical interface
Special Collection:
The Chemical Physics of the Electrode-Electrolyte Interface
H. Montes-Campos
;
H. Montes-Campos
a)
Grupo de Nanomateriais, Fotónica e Materia Branda, Departamento de Física de Partículas, Universidade de Santiago de Compostela
, Campus Vida s/n, E-15782 Santiago de Compostela, Spain
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A. Rivera-Pousa
;
A. Rivera-Pousa
Grupo de Nanomateriais, Fotónica e Materia Branda, Departamento de Física de Partículas, Universidade de Santiago de Compostela
, Campus Vida s/n, E-15782 Santiago de Compostela, Spain
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T. Méndez-Morales
T. Méndez-Morales
a)
Grupo de Nanomateriais, Fotónica e Materia Branda, Departamento de Física de Partículas, Universidade de Santiago de Compostela
, Campus Vida s/n, E-15782 Santiago de Compostela, Spain
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Note: This paper is part of the JCP Special Topic on The Chemical Physics of the Electrode–Electrolyte Interface.
J. Chem. Phys. 156, 014706 (2022)
Article history
Received:
November 02 2021
Accepted:
December 15 2021
Citation
H. Montes-Campos, A. Rivera-Pousa, T. Méndez-Morales; Density functional theory of alkali metals at the IL/graphene electrochemical interface. J. Chem. Phys. 7 January 2022; 156 (1): 014706. https://doi.org/10.1063/5.0077449
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