Superionic liquids in conducting nanoslits: A variety of phase transitions and ensuing charging behavior
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Author(s)
Dudka, Maxym
Kondrat, Svyatoslav
Bénichou, Olivier
Kornyshev, Alexei A
Oshanin, Gleb
Type
Journal Article
Abstract
We develop a theory of charge storage in ultranarrow slitlike pores of nanostructured electrodes. Our analysis is based on the Blume-Capel
model in an external field, which we solve analytically on a Bethe lattice. The obtained solutions allow us to explore the complete phase diagram
of confined ionic liquids in terms of the key parameters characterizing the system, such as pore ionophilicity, interionic interaction energy,
and voltage. The phase diagram includes the lines of first- and second-order, direct and re-entrant phase transitions, which are manifested
by singularities in the corresponding capacitance-voltage plots. Testing our predictions experimentally requires monodisperse, conducting
ultranarrow slit pores, to permit only one layer of ions, and thick pore walls, to prevent interionic interactions across the pore walls. However,
some qualitative features, which distinguish the behavior of ionophilic and ionophobic pores and their underlying physics, may emerge in
future experimental studies of more complex electrode structures.
model in an external field, which we solve analytically on a Bethe lattice. The obtained solutions allow us to explore the complete phase diagram
of confined ionic liquids in terms of the key parameters characterizing the system, such as pore ionophilicity, interionic interaction energy,
and voltage. The phase diagram includes the lines of first- and second-order, direct and re-entrant phase transitions, which are manifested
by singularities in the corresponding capacitance-voltage plots. Testing our predictions experimentally requires monodisperse, conducting
ultranarrow slit pores, to permit only one layer of ions, and thick pore walls, to prevent interionic interactions across the pore walls. However,
some qualitative features, which distinguish the behavior of ionophilic and ionophobic pores and their underlying physics, may emerge in
future experimental studies of more complex electrode structures.
Date Issued
2019-11-14
Date Acceptance
2019-10-10
Citation
The Journal of Chemical Physics, 2019, 151 (18)
ISSN
0021-9606
Publisher
AIP Publishing
Journal / Book Title
The Journal of Chemical Physics
Volume
151
Issue
18
Copyright Statement
© 2019 Author(s). American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 151, 184105 (2019); https://doi.org/10.1063/1.5127851 and may be found at https://doi.org/10.1063/1.5127851.
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/H004319/1
Subjects
Chemical Physics
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Publication Status
Published
Article Number
184105
Date Publish Online
2019-11-12