The distinction between diffusion-limited and non-diffusion-limited charge storage contributions from variable-rate cyclic or linear sweep voltammetry experiments is based on the fact that a diffusion-limited current i is proportional to the scan rate υ0.5 and a non-diffusion-limited current i is proportional to the scan rate υ. Therefore, a plot of i/υ0.5 vs. υ0.5 with the linear equation (Eq. 1) provides a slope a and an intercept b which reveal the diffusion-limited (faradaic) and non-diffusion-limited (capacitive and/or pseudocapacitive) contribution in a system with mixed charge storage processes. [1]
Eq. 1: i(υ) = aυ+bυ0.5
[1] Wang, J.; Polleux, J.; Lim, J.; Dunn, B., Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO2 (Anatase) Nanoparticles. The Journal of Physical Chemistry C 2007, 111 (40), 14925-14931.
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It should be noted that the faradaic and (pseudo)capacitive contribution will be determined for the first entered scan rate. Moreover, good linear regressions for every measurement point will be obtained if peak shifts are minimal.
| # | i/A () | i/A () | i/A () | i/A () | i/A () | i/A () | i(farad)/A | i(cap)/A | a(slope) | b(intercept) |
|---|---|---|---|---|---|---|---|---|---|---|
