Both thermal stability and electrical conductivity of alkali ion conducting Na2CO3 and Na2SO4, were improved by adding alkaline earth carbonates and sulfates, respectively, as well as insulating materials like gamma-Al2O3. The admiring of divalent compounds causes two effects. First a more or less extended solution can exist depending on the radius of the alkaline earth ion and is accompanied by an increase in electrical conductivity. Secondly, a phase mixture with an excess of dopant was observed that shows an enhancement in conductivity and mechanical stability. This phenomenon known as composite effect was observed in the following systems : Na2CO3-BaCO3, Na2CO3-SrCO3, Na2SO4-BaSO4, Na2SO4-gamma-Al2O3.