Molecular theory of solvation and electrical double layer in nanoporous carbon electrodes

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Proceedings titleElectrochemical capacitors, fundamentals to applications
Series titleECS Transactions; Volume 41
ConferenceElectrochemical Capacitors: Fundamentals to Applications - 220th ECS Meeting, October 9-14, 2011, Boston, MA, USA
Pages133149; # of pages: 17
SubjectElectrical double layers; Electrochemical capacitor; Electrochemical supercapacitor; Electrolyte solutions; Molecular theory of solvation; Nano-porous materials; Nanoporous carbon electrode; Quenched-annealed systems; Capacitors; Electric properties; Electrochemical electrodes; Morphology; Nanopores; Plasma interactions; Porous materials; Solvation; Statistical mechanics; Thermodynamics; Electrolytes
AbstractElectrical double layer (EDL) in a nanoporous electrode is very different from a planar electrochemical capacitor. The statistical-mechanical, molecular theory of solvation structure and thermodynamics (a.k.a. RISM-KH) is an essential part of multiscale methodology properly accounting for environment effects and chemical specificities of nanosystems in solution. Its generalization to solutions sorbed in disordered nanoporous materials using the replica method for statistical mechanics of quenched-annealed systems, replica RISM-KH-VM theory, provides full microscopic details of the solvation structure and thermodynamics as well as the electrochemical properties averaged over the thermal motion of sorbed solution and over quenched morphology of host nanoporous material. The replica RISM-KH-VM theory reveals the molecular mechanisms and driving forces of sorption of electrolyte solution in a nanoporous carbon electrode which are drastically different from the electrical double layer in electrolyte solution at a planar electrode. These include nanoporous confinement morphology and external charge, size and chemical specificities of solvent and electrolyte, osmotic forces, the internal EDL at the surface of nanopores and the external EDL at the contact with bulk solution. The interplay of these factors determines the efficiency of an electrosorption cell and the specific capacitance of the electrochemical supercapacitor.
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PublisherElectrochemical Society
AffiliationNational Research Council Canada (NRC-CNRC); National Institute for Nanotechnology
Peer reviewedYes
NPARC number21270220
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Record identifier5889eafc-850e-441b-8b67-e6096418b7e9
Record created2014-01-13
Record modified2016-05-09
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