dc.contributor.author | Yan, David | |
dc.contributor.author | Biesheuvel, P. M. | |
dc.contributor.author | Pugh, Mary C. | |
dc.contributor.author | Dawson, Francis P. | |
dc.contributor.author | Bazant, Martin Z | |
dc.date.accessioned | 2017-03-09T15:05:20Z | |
dc.date.available | 2017-03-09T15:05:20Z | |
dc.date.issued | 2017-03 | |
dc.date.submitted | 2017-01 | |
dc.identifier.issn | 2470-0045 | |
dc.identifier.issn | 2470-0053 | |
dc.identifier.uri | http://hdl.handle.net/1721.1/107242 | |
dc.description.abstract | Linear sweep and cyclic voltammetry techniques are important tools for electrochemists and have a variety of applications in engineering. Voltammetry has classically been treated with the Randles-Sevcik equation, which assumes an electroneutral supported electrolyte. In this paper, we provide a comprehensive mathematical theory of voltammetry in electrochemical cells with unsupported electrolytes and for other situations where diffuse charge effects play a role, and present analytical and simulated solutions of the time-dependent Poisson-Nernst-Planck equations with generalized Frumkin-Butler-Volmer boundary conditions for a 1:1 electrolyte and a simple reaction. Using these solutions, we construct theoretical and simulated current-voltage curves for liquid and solid thin films, membranes with fixed background charge, and cells with blocking electrodes. The full range of dimensionless parameters is considered, including the dimensionless Debye screening length (scaled to the electrode separation), Damkohler number (ratio of characteristic diffusion and reaction times), and dimensionless sweep rate (scaled to the thermal voltage per diffusion time). The analysis focuses on the coupling of Faradaic reactions and diffuse charge dynamics, although capacitive charging of the electrical double layers is also studied, for early time transients at reactive electrodes and for nonreactive blocking electrodes. Our work highlights cases where diffuse charge effects are important in the context of voltammetry, and illustrates which regimes can be approximated using simple analytical expressions and which require more careful consideration. | en_US |
dc.publisher | American Physical Society | en_US |
dc.relation.isversionof | http://dx.doi.org/10.1103/PhysRevE.95.033303 | en_US |
dc.rights | Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. | en_US |
dc.source | American Physical Society | en_US |
dc.title | Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes | en_US |
dc.type | Article | en_US |
dc.identifier.citation | Yan, David et al. “Theory of Linear Sweep Voltammetry with Diffuse Charge: Unsupported Electrolytes, Thin Films, and Leaky Membranes.” Physical Review E 95.3 (2017): n. pag. © 2017 American Physical Society | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemical Engineering | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Mathematics | en_US |
dc.contributor.mitauthor | Bazant, Martin Z | |
dc.relation.journal | Physical Review E | en_US |
dc.eprint.version | Final published version | en_US |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | en_US |
eprint.status | http://purl.org/eprint/status/PeerReviewed | en_US |
dc.date.updated | 2017-03-08T23:00:03Z | |
dc.language.rfc3066 | en | |
dc.rights.holder | American Physical Society | |
dspace.orderedauthors | Yan, David; Bazant, Martin Z.; Biesheuvel, P. M.; Pugh, Mary C.; Dawson, Francis P. | en_US |
dspace.embargo.terms | N | en_US |
mit.license | PUBLISHER_POLICY | en_US |