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A mechanistic model of the gas film dynamics during the electrochemical discharge phenomenon

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Abstract

A model for the prediction of the current–voltage characteristics of a two electrodes cell incorporating the dynamics of the gas film formed during the electrochemical discharge phenomenon is developed. In its mean-field version, the model presents good qualitative agreement but overestimates the hysteresis effect and predicts too large current densities for the cell operation once the gas film is formed. An improved stochastic model, which assumes gas film departures from the electrode surface according to a Poisson process, addresses these issues and gives significantly better predictions. Two relations are presented which allow estimating the mean gas film detachment time and its variance from the experimental study of the hysteresis in the forward and reverse scan of a two electrode cell operated at high current densities.

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Abbreviations

A :

Electrode surface (m2)

F :

Faraday constant (C mol−1)

h b :

Effective average bubble height (m)

I :

Current (A)

j crit :

Nominal critical current density, nominal current density at which a gas film can be formed (A m−2)

j local :

Local current density (A m−2)

N :

Number of lattice sites per surface (m−2)

n :

Stoichiometric number

n s :

Average normalised number (per total number of lattice sites) of clusters of size s

P :

Average size of infinite cluster (in number of sites per total number of sites in the lattice)

p :

Pressure (Pa)

p c :

Percolation threshold

R :

Ideal gas constant (J K−1 mol−1)

R(θ):

Inter-electrode resistance (with the presence of bubbles) (Ω)

R bulk :

Bulk inter-electrode resistance (without the presence of bubbles) (Ω)

s :

Cluster size (in number of lattice sites)

T :

Temperature (K)

t :

Time (s)

t f :

Average gas film formation time (s)

U :

Cell terminal voltage (V)

U crit :

Critical voltage, voltage at which a gas film can be formed (V)

U d :

Water decomposition potential (V)

V b :

Volume of a gas bubble of size s = 1 (m3)

\( \dot{V}_{g} \) :

Gas volume per unit of time (m3 s−1)

v :

Voltage scan rate (V s−1)

z :

Charge number

β :

Coefficient of Faradic gas production (m3 s−1 A−1)

θ :

Electrode surface bubble coverage

Δt b :

Average bubble detachment time (s)

Δt g :

Average gas film detachment time (S)

Over lined:

Normalised quantities

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Acknowledgments

This work was supported by the Natural Sciences and Engineering Research Council of Canada (NSERC).

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Authors and Affiliations

  1. Department of Mechanical and Industrial Engineering, Concordia University, Montreal, QC, Canada

    R. El-Haddad & R. Wüthrich

Authors
  1. R. El-Haddad
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  2. R. Wüthrich
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Correspondence to R. Wüthrich.

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Dedicated to Prof. Ch. Comninellis’ 65th birthday.

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El-Haddad, R., Wüthrich, R. A mechanistic model of the gas film dynamics during the electrochemical discharge phenomenon. J Appl Electrochem 40, 1853–1858 (2010). https://doi.org/10.1007/s10800-010-0141-7

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  • DOI: https://doi.org/10.1007/s10800-010-0141-7

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