The electroneutrality approximation in electrochemistry

Dickinson, Edmund J. F.; Limon-Petersen, Juan G.; Compton, Richard G.

doi:10.1007/s10008-011-1323-x

Cited by 73 publications

(68 citation statements)

References 45 publications

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“…More recently, Compton and co-workers have done extensive work involving theory [66][67][68], simulations [37,66,69,70] (and see Chap. 7 of [3] or Chap.…”

Section: Historical Reviewmentioning

confidence: 99%

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

Yan

Bazant

Biesheuvel³

et al. 2017

Phys. Rev. E

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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 PoissonNernst-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.

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“…More recently, Compton and co-workers have done extensive work involving theory [66][67][68], simulations [37,66,69,70] (and see Chap. 7 of [3] or Chap.…”

Section: Historical Reviewmentioning

confidence: 99%

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

Yan

Bazant

Biesheuvel³

et al. 2017

Phys. Rev. E

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“…A comprehensive review can be found in. 13 The influence of the electro-neutrality approximation on steady-state voltammetry has been investigated in. 14,15 The steady-state analysis for the lead-acid batteries was performed in.…”

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confidence: 99%

On the Deviation of Electro-Neutrality in Li-Ion Battery Electrolytes

Rademaker

Akkermans

Danilov

et al. 2014

J. Electrochem. Soc.

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The electro-neutrality assumption for Li-ion battery electrolytes has been mathematically investigated. A general system of equations describing the development of ionic concentration gradients in simple binary electrolytes is derived. Considering that the overpotentials and the concentration gradients across the electrolyte are most dominant under steady-state (dis)charging, the analyzes have been performed under these limiting conditions. It was found that deviations from electro-neutrality in terms of ionic concentrations are extremely small and do not exceed 10−7% under normal (dis)charging conditions. Nevertheless this small deviation is responsible for development of an electric field with considerable magnitude. Therefore, a rearrangement of standard Nernst-Planck equations is essential to accurately model these processes at different scales.

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“…In the literature one often employs the so-called local electroneutrality approximation (LEN) [23,24] because it avoids the effort of finding the solution of Eq. (7) which is not known in closed analytical form.…”

Section: Model System and Reduction To A One-dimensional Effective Prmentioning

confidence: 99%

Steric Modulation of Ionic Currents in DNA Translocation Through Nanopores

2014

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Ionic currents accompanying DNA translocation strongly depend on molarity of the electrolyte solution and the shape and surface charge of the nanopore. By means of the Poisson–Nernst–Planck equations it is shown how conductance is modulated by the presence of the DNA intruder and as a result of competing electrostatic and confinement factors. The theoretical results reproduce quantitatively the experimental ones and are summarized in a conductance diagram that allows distinguishing the region of reduced conductivity from the region of enhanced conductivity as a function of molarity and the pore dimension

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The electroneutrality approximation in electrochemistry

Cited by 73 publications

References 45 publications

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

Theory of linear sweep voltammetry with diffuse charge: Unsupported electrolytes, thin films, and leaky membranes

On the Deviation of Electro-Neutrality in Li-Ion Battery Electrolytes

Steric Modulation of Ionic Currents in DNA Translocation Through Nanopores

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