Testing Electrochemical Capacitors with CV

Simulating Cyclic Voltammetry

One of the problems that faced early electrochemists interested in current-potential-time relationships in cyclic voltammetry was the complexity of the diffusion equations. Sevcik [ Coll Czech Chem Comm, 13 (1948) 349 ] derived a series approximation for the current-potential curve in CV, but cyclic voltammetry got a big boost as a mechanistic tool from the landmark series of publications by Nicholson and Shain [ Anal Chem, 36 (1964) 706 ].

Nicholson solved the x-dependence of the diffusion equation via Laplace Transforms but was then left with an integral equation for current vs. E. He numerically integrated this equation for various values of sweep rate and kinetic parameters and published ‘working curves’ for others to use without having to repeat the (then) tedious calculations.

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