Electrolysis in a closed electrochemical cell with a small inter-electrode distance. Metal dissolution/deposition in plain electrolytes

Zelinsky, A.G.; Pirogov, B.Ya.

doi:10.1016/j.electacta.2009.06.080

Cited by 12 publications

(14 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…24 To circumvent this problem a vast amount of previous work assumes electro-neutrality throughout the complete electrolyte phase, thus neglecting the DLs. [3][4][5][6]16,25,26 The DLs, however, cannot be neglected as they influence the charge transfer rate at the electrodes and make significant contribution to the cell voltage. 23,[27][28][29][30][31][32][33][34] To describe Faradaic reaction rates at the electrodes, it is reasonable to assume that the charge transfer occurs at some atomic distance away from the electrodes, at the "reaction plane" (for an atomically flat electrode), which serves as the edge of the continuum region representing the electrolyte (Fig.…”

Section: Introductionmentioning

confidence: 99%

Diffuse-charge effects on the transient response of electrochemical cells

2010

View full text Add to dashboard Cite

We present theoretical models for the time-dependent voltage of an electrochemical cell in response to a current step, including effects of diffuse charge ͑or "space charge"͒ near the electrodes on Faradaic reaction kinetics. The full model is based on the classical Poisson-Nernst-Planck equations with generalized FrumkinButler-Volmer boundary conditions to describe electron-transfer reactions across the Stern layer at the electrode surface. In practical situations, diffuse charge is confined to thin diffuse layers ͑DLs͒, which poses numerical difficulties for the full model but allows simplification by asymptotic analysis. For a thin quasiequilibrium DL, we derive effective boundary conditions on the quasi-neutral bulk electrolyte at the diffusion time scale, valid up to the transition time, where the bulk concentration vanishes due to diffusion limitation. We integrate the thin-DL problem analytically to obtain a set of algebraic equations, whose ͑numerical͒ solution compares favorably to the full model. In the Gouy-Chapman and Helmholtz limits, where the Stern layer is thin or thick compared to the DL, respectively, we derive simple analytical formulas for the cell voltage versus time. The full model also describes the fast initial capacitive charging of the DLs and superlimiting currents beyond the transition time, where the DL expands to a transient non-equilibrium structure. We extend the well-known Sand equation for the transition time to include all values of the superlimiting current beyond the diffusion-limiting current.

show abstract

Section: Introductionmentioning

confidence: 99%

Diffuse-charge effects on the transient response of electrochemical cells

2010

View full text Add to dashboard Cite

show abstract

“…For small potential drops across the Stern layer, which e.g. occur in case of fast electrode kinetics, we can lin earize the Faradaic current, such that (27) where i* = k R -j O , which after substitution into Eq. (24) and integration results in, (28) for the potential drop across the Stern layer, where the ± sign again refers to the positive value at position x = 1 and the negative value at position x = 0.…”

Section: Debye Harmonic and Diffusion Time Scalementioning

confidence: 99%

“…The assumption of electroneutrality to describe mass transfer is ubiquitous in the literature of electro chemistry [21][22][23][24][25][26][27][28]. Considering Poisson's equation, i.e.…”

Section: Generalized Frumkin-butler-volmer Equationmentioning

confidence: 99%

“…As a result we have large electrical field strengths in this layer, while ion concentration gradients counter the forces acting on the ions due to these electrical fields. Includ ing the DLs in an electrochemical model goes beyond the common assumption of electroneutrality, which is ubiquitous in the literature of electrochemical model ing [21][22][23][24][25][26][27][28]. However, including diffuse layers might be important as the electrical potential and ion con centration gradients in these nanoscopic layers are large compared to the more gradual changes in the electroneutral bulk electrolyte.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Frumkin-Butler-Volmer theory and mass transfer in electrochemical cells

Soestbergen

2012

Russ J Electrochem

View full text Add to dashboard Cite

Abstract-An accurate mathematical description of the charge transfer rate at electrodes due to an electro chemical reaction is an indispensable component of any electrochemical model. In the current work we use the generalized Frumkin Butler-Volmer (gFBV) equation to describe electrochemical reactions, an equa tion which, contrary to the classical Butler-Volmer approach, includes the effect of the double layer compo sition on the charge transfer rate. The gFBV theory is transparently coupled to the Poisson-Nernst-Planck ion transport theory to describe mass transfer in an electrochemical cell that consists of two parallel plate electrodes which sandwich a monovalent electrolyte. Based on this theoretical approach we present analytical relations that describe the complete transient response of the cell potential to a current step, from the first initial capacitive charging of the bulk electrolyte and the double layers all the way up to the steady state of the system. We show that the transient response is characterized by three distinct time scales, namely; the capac itive charging of the bulk electrolyte at the fastest Debye time scale, and the formation of the double layers and the subsequent redistribution of ions in the bulk electrolyte at the longer harmonic and diffusion time scales, respectively.

show abstract

“…In this method, the electrolyte flow through the electrode surface. According to its high mass transfer rate and refresh electrode surface, the flowing electrolysis has been used for waste water treatment [32,33], electrochemical detector [34,35] and reaction kinetics study [36][37][38]. Herein, a novel flowing electrolysis method was developed for the preparation of carbon nanomaterials.…”

Section: Introductionmentioning

confidence: 99%

Flowing electrolytic synthesis of fluorescent carbon nanoparticles and carbon nanosheets

Shen

2015

Electrochimica Acta

View full text Add to dashboard Cite

Electrolysis in a closed electrochemical cell with a small inter-electrode distance. Metal dissolution/deposition in plain electrolytes

Cited by 12 publications

References 19 publications

Diffuse-charge effects on the transient response of electrochemical cells

Diffuse-charge effects on the transient response of electrochemical cells

Frumkin-Butler-Volmer theory and mass transfer in electrochemical cells

Flowing electrolytic synthesis of fluorescent carbon nanoparticles and carbon nanosheets

Contact Info

Product

Resources

About