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Title: Evaluation of the constant potential method in simulating electric double-layer capacitors

A major challenge in the molecular simulation of electric double layer capacitors (EDLCs) is the choice of an appropriate model for the electrode. Typically, in such simulations the electrode surface is modeled using a uniform fixed charge on each of the electrode atoms, which ignores the electrode response to local charge fluctuations in the electrolyte solution. In this work, we evaluate and compare this Fixed Charge Method (FCM) with the more realistic Constant Potential Method (CPM), [S. K. Reed et al., J. Chem. Phys. 126, 084704 (2007)], in which the electrode charges fluctuate in order to maintain constant electric potential in each electrode. For this comparison, we utilize a simplified LiClO{sub 4}-acetonitrile/graphite EDLC. At low potential difference (ΔΨ ⩽ 2 V), the two methods yield essentially identical results for ion and solvent density profiles; however, significant differences appear at higher ΔΨ. At ΔΨ ⩾ 4 V, the CPM ion density profiles show significant enhancement (over FCM) of “inner-sphere adsorbed” Li{sup +} ions very close to the electrode surface. The ability of the CPM electrode to respond to local charge fluctuations in the electrolyte is seen to significantly lower the energy (and barrier) for the approach of Li{sup +} ions to the electrodemore » surface.« less
Authors:
;  [1] ; ; ;  [2]
  1. Department of Chemistry, University of Kansas, Lawrence, Kansas 66045 (United States)
  2. Department of Materials Science and Engineering, University of California, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22415336
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 18; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACETONITRILE; COMPARATIVE EVALUATIONS; DENSITY; ELECTRIC POTENTIAL; ELECTRODES; ELECTROLYTES; GRAPHITE; ION DENSITY; LITHIUM IONS; LITHIUM PERCHLORATES; SIMULATION; SOLUTIONS; SOLVENTS; SURFACES