Reference electrode formation in potentiometric CO2 sensors with alkali ion conducting alumosilicate glasses as solid electrolytes

Potentiometric CO₂ gas sensors with Li conducting glasses/glass ceramics of the system Li₂O-Al₂O₃-SiO₂ (different nominal composition) as solid electrolytes have been investigated. Li₂CO₃ was used as CO₂ and O₂ sensitive auxiliary electrode. During the sensor test measurements, the CO₂ partial pressure was varied between 1×10⁻³ and 1×10⁻¹ bar at a constant O₂ partial pressure of 2.1×10⁻¹ bar whereas N₂ was used as carrier gas. Comparative measurements were accomplished with sensors comprising Na and K ion conducting glasses. A metastable reference electrode was formed at the contact zone between the Au metal electrode and the former Li glasses of definite nominal composition by crystallization processes taking place, which lead to stable, reproducible CO₂ dependent EMF signals for more than 90d. The thermodynamically expected EMF difference and the observed EMF difference agree quite well between 500 and 600 °C. At 600 °C, the drift of sensors with glasses as solid electrolytes and direct Au glass/glass ceramics contact as reference electrode amounts typically 0.32 mV/d (p(CO₂)=1×10⁻³ bar, p(O₂)=2.1×10⁻¹ bar at the measuring electrode), if a metastable multiphase equilibrium is formed. At identical partial pressures of CO₂ and O₂, the signal reproducibility of these sensors with different solid electrolyte glasses of the same nominal composition lies within 30 mV at 600 °C. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996