电动势与热动力学 燃料电池.pptVIP

2011 SpringFuel Cell and Electrochemistry Lecture 11 Potentials and Thermodynamics of Cells Reversibility 1)Chemical Reversibility Pt is 0.222V more negative than Ag Shorted External battery chemically reversible: Reversing the cell current merely reverses the cell reaction. No new reactions appear, thus the cell is termed; chemically irreversible: different electrode reactions as well as a different net process upon current reversal; Reversibility Thermodynamically reversible: when an infinitesimal reversal in a driving force causes it to reverse direction In electrochemistry If a system follows the Nernst equation or an equation derived from it, the electrode reaction is often said to be thermodynamically or electrochemically reversible (or nernstian). Free Energy and Cell emf Reduction Potentials The primary reference, chosen by convention, is the normal hydrogen electrode (NHE), also called the standard hydrogen electrode (SHE): emf and Concentration Reference Electrodes Introduction IS measures the resistance of a circuit to an applied voltage Z(t) = E(t)/I(t), Z(?)=E(?)/I(?) When E is applied as a sinusoidal function in a linear system, I response can be represented by a sum of sinusoidal fuctions with phase shifts. If an equivalent circuit for the system being probed can be constructed, then the resistance or capacitance values for each circuit element can be backed out from Z. Background – Impedance and Circuit Elements E(t) = E0cos(?t), ?=2?f I(t) = I0 cos(?t-?) Or, if one writes in complex notation: E(t) = E0 exp(i?t) I(t) = I0 exp(i?t - i?) Z(t) = Z0 exp(i?) = Z0 (cos ? + isin ?) Plotting Impedance ? Plotting Impedance Circuit Elements from Electrochemistry Electrolyte resistance Double layer capacitance (~30?F/cm2 for aqueous systems) Polarization resistance Charge transfer resistance Coating capacitance Constant phase element (a fudge factor) Virtual inductor (adsorption?) And… Diffusion (aka Warburg Impedance) Warburg impedan