Synthesis and thermal stability of (Co,Ni)O solid solutions

(Co,Ni)O solid solutions are considered as promising protective materials of O₂-evolving anodes for Al production. In this context, two solid-state synthesis methods, namely high-energy ball milling (HEBM) and calcination, have been evaluated for the synthesis of (Co,Ni₎O solid solutions. In all cases, Co_xNi_1?xO solid solutions can be formed over the whole composition range. However, undesired WC contaminant is observed using the HEBM method due to the erosion of the milling tools. Their thermal stability in air has been analyzed by thermogravimetric analyzes (TGA) complemented by X-ray diffraction (XRD) analyses. It is shown that Co_xNi_1?xO solid solutions are stable at 1000°C over the whole composition range whereas they are only stable for x ≤ 46 and x ≤ 22 at 800°C and 700°C, respectively. For higher Co contents, the formation of Co₃O₄ is observed. This is a relevant information for their future use for Al production, which can be done at different temperatures (~700-1000°C) depending of the electrolyte composition.