Rate-Limiting Steps Elucidated By Electrochemical Impedance Spectroscopy of a Yttria-Stabilized Zirconia 2-in-1 Temperature and Oxygen Gas Sensor Measured at Extreme Temperatures
Authors: Peters Travis L , Lin Jiaji , Akbar Sheikh Ali , Modroukas Dean 
Published: May 2020

Introduction

Yttria-stabilized zirconia (YSZ) is known for its good ionic conductivity, essentially being synonymous with the term “lambda sensor”. Automotive lambda sensors have been fabricated with YSZ as the electrolyte for 30+ years and have operated in a temperature region of 600oC to 800oC. There is an increasing demand for higher operating temperature sensors, specifically a 2-in-1 temperature and oxygen sensor which is stable, selective, and sensitive in extreme environments. However, there remains a disagreement among scholars about the effects on oxygen vacancy activation energy at temperatures higher than 800oC. Also, the rate-limiting step of oxygen reduction on the platinum electrode is not inherently clear. A 2-in-1 temperature and oxygen sensor was fabricated and characterized with the analysis of electrochemical impedance spectroscopy (EIS), DC resistance, and open circuit potential measurements at temperatures between 600oC and 1200oC. The temperature dependence on individual activation energies within the sensor was elucidated directly through these techniques.

Methods

Yttria-stabilized zirconia (MTI Corp) was employed as the solid-state electrolyte in sensor fabrication, with the primary electrode material as porous platinum (ESL 5570). Platinum paste was screen printed onto planar YSZ substrates in an interdigitated electrode configuration, then fired at 1500oC for 2 hours in nitrogen atmosphere (1 atm). The sensor was placed in a ThermoScientific tube furnace capable of reaching 1500oC, with mass flow controllers varying oxygen gas concentration throughout electrical measurements. Platinum foil acted as a Faraday cage around the sensor to shield from furnace inductive fluctuations and minimize noise during low frequency EIS measurements. A thermocouple placed next to the sensor validated furnace operating temperature and cooling endcaps on the furnace tube created a natural temperature gradient between sensor placement and the electrical connections outside of the furnace. Figure 1 displays the environmental testing setup.

Results and Conclusions

Figure 2a displays an impedance Nyquist spectrum that contains real and imaginary components of impedance measured at 0.21 atm PO2, where electrolyte resistance decreases with an increase in temperature. Figure 2b displays the Arrhenius plot of isolated YSZ electrolytic resistance extracted from figure 2a, where there are distinct activation regions at moderate and high temperatures. In agreement with Badwal [1], the shift to lower EA at higher temperatures was due to a gradual transition between an association region where oxygen vacancies are bound to dopant cations, and a dissociation region where vacancies are free and mobile.
At a known temperature, EIS also elucidates oxygen concentration dependence on sensor electrode resistance. Figure 3a shows sensor electrode resistance, fitted from figure 2a, as a function of oxygen concentration. Investigating the oxygen reduction reaction (ORR) variation on platinum at various temperature regions, it is suggested that ORR on platinum is co-limited by oxygen adsorption and by oxygen transport along the surface of the electrode, in agreement with Adler [2]. Figure 3b shows that electrode 2 is dominant at temperatures below 1050oC, indicative of oxygen diffusion limitation on the surface and through platinum. Electrode 1 is dominant at temperatures above 1050oC, where dissociative adsorption of oxygen on the electrode surface is predominant.

References

[1] S. P. S. Badwal, “Electrical conductivity of single crystal and polycrystalline yttria-stabilized zirconia,” J. Mater. Sci., vol. 19, pp. 1767–1776, 1984.
[2] S. B. Adler, “Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes †,” Chem. Rev., vol. 104, pp. 4791–4843, 2004.

Figure 1