期刊
MONATSHEFTE FUR CHEMIE
卷 140, 期 9, 页码 1113-1119出版社
SPRINGER WIEN
DOI: 10.1007/s00706-009-0130-x
关键词
Impedance spectroscopy; Mixed conductor; Chemical diffusion; Hebb-Wagner polarization; Space-charge polarization; Adsorption capacitance
资金
- Korean Government (MOEHRD) [KRF-2008-531-D00006]
The generalized equivalent circuit for Hebb-Wagner polarization in the frequency domain proposed by Jamnik and Maier (J Electrochem Soc 146:4183, 1999) includes the space-charge polarization that was previously neglected. In the present work, using a self-coded Fortran program, the completely generalized equivalent circuit is successfully applied to a mixed conducting silver sulfide with an AgI electrode that suppresses the electronic flow. A whole set of fit parameters, such as geometric capacitance, partial conductivities, chemical capacitance or diffusivity, and the blocking and shunting characteristics of electrodes are independently but self-consistently obtained over a range of silver activities, as controlled by a galvanic cell. The interfacial capacitance was found to be much larger than the diffuse space-charge double-layer capacitance and was thus ascribed to the adsorption capacitance at the core of the interface, which should be connected in parallel with the space-charge double-layer polarization. Two simplified equivalent circuits were shown to be good approximations for the spectra at the extreme low and high silver activity, respectively.
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