Concentration Fluctuations and Capacitive Response in Dense Ionic Solutions

Publication Year
2016

Type

Journal Article
Abstract
We use molecular dynamics simulations in a constant potential ensemble to study the effects of solution composition on the electrochemical response of a double layer capacitor. We find that the capacitance first increases with ion concentration following its expected ideal solution behavior but decreases upon approaching a pure ionic liquid in agreement with recent experimental observations. The nonmonotonic behavior of the capacitance as a function of ion concentration results from the competition between the independent motion of solvated ions in the dilute regime and solvation fluctuations in the concentrated regime. Mirroring the capacitance, we find that the characteristic decay length of charge density correlations away from the electrode is also nonmonotonic. The correlation length first decreases with ion concentration as a result of better electrostatic screening but increases with ion concentration as a result of enhanced steric interactions. When charge fluctuations induced by correlated ion-solvent fluctuations are large relative to those induced by the pure ionic liquid, such capacitive behavior is expected to be generic.
Journal
Journal of Physical Chemistry Letters
Volume
7
Pages
2333-2338
Date Published
07/2016
Type of Article
Article
ISBN
1948-7185
Accession Number
WOS:000379457400007
Short Title
J. Phys. Chem. Lett.J. Phys. Chem. Lett.
Alternate Journal
J. Phys. Chem. Lett.

ISI Document Delivery No.: DQ8JPTimes Cited: 9Cited Reference Count: 43Uralcan, Betul Aksay, Ilhan A. Debenedetti, Pablo G. Limmer, David T.Multidisciplinary University Research Initiative (MURI) through the Air Force Office of Scientific Research [FA9550-13-1-0004]; Princeton Center for Theoretical Science; National Science Foundation [CBET-1263565, CHE-1213343]We would like to thank Benjamin Rotenberg for useful comments on an earlier version of this manuscript. This work was supported in part by a Multidisciplinary University Research Initiative (MURI) through the Air Force Office of Scientific Research (Grant FA9550-13-1-0004). D.T.L. was supported by the Princeton Center for Theoretical Science. P.G.D. acknowledges the support of the National Science Foundation (Grant Nos. CBET-1263565 and CHE-1213343).9428Amer chemical socWashington