Interfacial effects in electrochemical cells for oxygen ionic conduction measurements I. The e.m.f. method

被引：92

作者：

Kharton, VV ^{[1
]}

Marques, FMB ^{[1
]}

机构：

[1] Univ Aveiro, UIMC, Dept Ceram & Glass Engn, P-3810193 Aveiro, Portugal

来源：

SOLID STATE IONICS | 2001年 / 140卷 / 3-4期

关键词：

mixed conductor; potentiometry; transference number; polarization resistance; solid electrolyte;

D O I：

10.1016/S0167-2738(01)00851-7

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Significant electrode polarization leads to the underestimation of apparent oxygen ion transference numbers of mixed ionic-electronic conductors, determined by measurement of either e.m.f. of oxygen concentration cells or Faradaic efficiency. In addition to e.m.f. data under open-circuit conditions, the exact measurement of the transference numbers requires no less than two parameters describing the system such as oxygen permeation flux, bulk resistance, voltage or current under closed-circuit conditions. Selected examples of experimental routes, aimed at taking electrode polarization into account, are considered. An appropriate choice of experimental procedures used in e.m.f. or Faradaic efficiency measurements, in combination with the use of electrodes with high polarization resistance, enables significant accuracy improvement in the determination of very small electronic contributions to the total conductivity. For potentiometric oxygen sensors, the presence of minor electronic conduction was shown to result in great experimental errors in the oxygen partial pressure measurement if the polarization resistance of sensor electrodes is high. Analogously, minor electronic conductivity in solid electrolytes may lead to a large error of the polarization resistance determination by impedance spectroscopy in conditions where the polarization resistance significantly exceeds the bulk resistance of the electrolyte. (C) 2001 Elsevier Science B.V. All rights reserved.

引用

页码：381 / 394

页数：14

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