Silver/Silver Chloride Electrode: Charging of a Porous Structure

Szpak, S.; Nedoluha, A.; Katan, T.

doi:10.1149/1.2134394

Cited by 8 publications

(6 citation statements)

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“…By combining ( 16) and ( 17), analagous to the combination of ( 7) and ( 8), ( 18) now expresses dO/dt as a function of time /" = 50 x 10"cm and j = 35 xlO _8 mV~'s ' obtained by a best-fit method. Then, the current was calculated as a function of i/ by (17).…”

Section: R S +mentioning

confidence: 99%

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The kinetics of silver bromide film formation on the silver anode

Birss

Wright

1982

Electrochimica Acta

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The anodic potentiodynamic formation of an AgBr film on an Ag rotating disc electrode was studied in aqueous bromide solutions. As the electron transfer step (1) is intrinsically fast, Ag + Br ^AgBr + c",and as the film remains porous throughout its growth, the rate of film growth is limited by physical parameters such as ionic diffusion and migration in the solution.The anodic E/I curves for AgBr film formation were calculated quantitatively by computer on the basis of the following model of film growth. Film formation occurs initially by the nucleation of islands of film to a critical thickness, and then these islands spread laterally until only small pores remain between them. As these pores become small, the resistance of the solution within them becomes rate limiting (at the anodic current peak). After the peak, the concentration of bromide ions at the pore base falls to zero and current is then controlled by the diffusion of bromide ions into the lengthening pores of the film.This lateral spreading mechanism and the subsequent retention of the porous film morphology has been substantiated by comprehensive Scanning Electron Microscope investigations.

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Section: R S +mentioning

confidence: 99%

“…Therefore, the diffusion current can now be expressed as in (19). which can then be rearranged to give an expression for C s (20), where / is obtained from (17).…”

Section: R S +mentioning

confidence: 99%

The kinetics of silver bromide film formation on the silver anode

Birss

Wright

1982

Electrochimica Acta

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“…Manuscript submitted Jan. 9, 1976; revised manuscript received April 6, 1976. This was Paper 55 presented at the Dallas, Texas, Meeting of the Society, Oct. [5][6][7][8][9] 1975.…”

Section: Acknowledgmentmentioning

confidence: 99%

“…Nevertheless, such experiments have now progressed Mong two paths: those dealing directly with idealized single pores (2)(3)(4) and those treating aggregates of pores in model porous electrodes more or less representing a real battery electrode (5)(6)(7)(8)(9)(10).…”

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confidence: 99%

“…Model electrodes having some resemblance to real electrodes have been studied with varying degrees of success in understanding the prevailing reaction modes and distributions, i.e., by Alkire et al for the Cu/CuSO4 system (5,6), by Bro and Kang for Cd/Cd(OH)e (7), by Nagy and Bockris for Zn/Zn (OH)~ (8), by Szpak et al for Ag/AgC1 (9), and by Simonsson for PbSO4/ PbO2 (10). In some of these studies electrodes were cut into sections after charging or discharging, and the current distribution was inferred from the amount of chemical change that occurred in each section.…”

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Analysis of Porous Electrodes with Sparingly Soluble Reactants: IV . Application to Particulate Bed Electrode: System

Katan

Bennion

1976

J. Electrochem. Soc.

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Experiments were conducted to characterize critical processes which determine performance of totally immersed, porous, secondary electrodes having sparingly soluble reactants. Particulate beds comprised of silver spheres, 37.7 -+-4.2 ~m in diameter, were used as Ag/AgC1 electrodes in 1N KC1. Silver chloride product distribution and facial potential as functions of time during galvanostatic charging are compared to predictions of a recently developed mathematical model. Good accord is shown over the tested time range, 1-19 rain, and exterior current density 50 mA cm-~. Time for onset of pore blockage with failure to accumulate charge, about 18 rain, and the reaction penetration, mostly less than 0.03 era, are predicted with reasonable accuracy. A characteristic minimum in polarization occurs during galvanostatic discharge due to reduction in pore blockage at the beginning of discharge, increase in KC1 concentration in the depth of the electrode, and increase in effective matrix electronic conductivity with silver deposition. A final rise in polarization occurs when silver chloride is depleted. Theory is used to show how governing rate processes are shifted by the occurrence of blockages of the first and second kinds.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.6.218.72 Downloaded on 2015-06-06 to IP Vol. 123, No. 9 ANALYSIS OF POROUS ELECTRODES Basis of parameter selection Measured Approximate measured value Measured Measured Estimated from photomicrographs Approximate, measured value, Ref. (13)Calculated from porosity and sphere diameter, Ref. (15) Calculated from porosity and sphere diameter, Ref. (15) Calculated from estimated diffusion coefficient, Ref. (12), and diffusion path, Ref. (13) Best value fitting data From Ref. (12) where A is specific surface area in era-1 and from assumption of 0.9 coverage factor, Fig. 8 Assumed functional dependence and mode change at 0.9, Fig. 8 Geometrical reasoning, e.g., Ref. (21)9 A parabolic decrease with distance is a~sumed for the porosity change at depths from 0 to 0.45 mm as an approximation based o• photomicrographs. 9 * Surface is calculated according to ReL (15) from the porosity and sphere radius for depths from 0 to 0.45 ram.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.6.218.72 Downloaded on 2015-06-06 to IP

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