Diffusion to rough interfaces: finite charge transfer rates

Chronoammetry and Chronopotentiometry on Electrodes with a Microrough Surface: Theoretical Consideration

“…The fractal approach was developed for porous, dendrite-like, and other electrodes with a complex surface morphology [7,8] and will not be considered in this work. Non-fractal approach implies the electrode surface description with a certain function ξ ( x , y ) , which depends not only on the lateral coordinates x and y , but also on a number of constants or random morphological parameters [9][10][11][12][13][14][15][16][17]. The solution of the corresponding transient diffusion problem enables one to calculate the concentration field c ( x , y , z , t ) provided that at least one boundary condition is set at z = ξ ( x , y ) , where z axis is directed from the electrode surface to the bulk solution.…”

The cell-impedance-controlled lithium transport through LiMn2O4 film electrode with fractal surface by analyses of ac-impedance spectra, potentiostatic current transient and linear sweep voltammogram

“…Moreover, it has also been concluded [24][25][26][27] that hydrogen transport through the hydride-forming electrodes such as Pd and metal hydrides proceeds under the condition where hydrogen diffusion in the electrode is kinetically mixed with the charge-transfer reaction at the electrode/electrolyte interface. In these cases, it is obvious that classical fractal theories derived under the diffusion-controlled constraint place a limitation on describing mass transport through the fractal electrode under the constraint of mixed control [28,29].…”

Self-affine roughness influence on redox reaction charge admittance

“…In the more general case, the power-law flux transient on a fractal interface with Euclidean dimension D E of the embedding space has the form c = ( [8,12,13]. Other general results were obtained in understanding the effect of roughness on the interfacial reaction current in terms of an arbitrary weak roughness profile and an arbitrary roughness power spectrum [18][19][20][21]23] without however addressing the questions related to finite scale-invariant interfaces.…”

“…[8,9]. The frequency response of rough interface depends on the regime under consideration such as for example (i) the capacitive behavior of rough electrodes [24][25][26][27][28][29][30][31][32][33][34][35][36], and (ii) diffusion controlled charge transfer on rough interfaces [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26].…”

“…Studies related to transport to and across a rough interface are of general interest in a wide variety of research fields as for example spin relaxation [1], fluorescence quenching [1,2], heterogeneous catalysis [3], enzyme kinetics [4], heat diffusion [5], membrane transport [6,7], and electrochemistry [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26]. In the latter case, the exploration of the mechanism of interfacial processes and the evaluation of parameters such as double-layer capacitance and charge rate constants can be performed by impedance spectroscopy [8,9].…”