Corrosion testing of zirconia, beryllia and magnesia ceramics in molten alkali metal carbonates at 900 °C

An electrochemical cell containing molten Li₂CO₃-Li₂O at 900 °C has been proposed for the conversion of the greenhouse gas CO₂ to CO for chemical energy storage. In the current work, we have examined the corrosion resistance of zirconia, beryllia and magnesia ceramics at 900 °C in the Li₂CO₃-Li₂O and Li-Na-K carbonate eutectic mixtures to identify suitable electrically insulating materials. Conclusions regarding material stability were based on elemental analysis of the melt, primarily via X-ray photoelectron spectroscopy, a particularly sensitive technique. It was found that magnesia is completely stable for at least 33 h in a Li₂CO₃-Li₂O melt, while a combined lithium titanate/lithium zirconate layer forms on the zirconia ceramic as detected by XRD. Under the same melt conditions, beryllia shows considerable leaching into solution. In a Li-Na-K carbonate eutectic mixture containing 10.2 mol% oxide at 900 °C under standard atmospheric conditions, magnesia showed no signs of degradation. Stabilization of the zirconia content of the eutectic mixture at 0.01-0.02 at% after 2 h is explained by the formation of a lithium zirconate coating on the ceramic. On the basis of these results, we conclude that only magnesia can be satisfactorily used as an insulating material in electrolysis cells containing Li₂CO₃-Li₂O melts.