Phase diagram, crystal chemistry and thermoelectric properties of compounds in the Ca–Co–Zn–O system

In the Ca–Co–Zn–O system, we have determined the tie-line relationships and the thermoelectric properties, solid solution limits, and structures of two low-dimensional cobaltite series, Ca3(Co, Zn)4O9−z and Ca3(Co,Zn)2O6−z at 885 °C in air. In Ca3(Co,Zn)4O9−z, which has a misfit layered structure, Zn was found to substitute in the Co site to a limit of Ca3(Co3.8Zn0.2)O9−z. The compound Ca3(Co,Zn)2O6−z (n=1 member of the homologous series, Can+2(Co,Zn)n(Co,Zn)′O3n+3−z) consists of one-dimensional parallel (Co,Zn)2O66− chains that are built from successive alternating face-sharing (Co,Zn)O6 trigonal prisms and ‘n’ units of (Co,Zn)O6 octahedra along the hexagonal c-axis. Zn substitutes in the Co site of Ca3Co2O6 to a small amount of approximately Ca3(Co1.95Zn0.05)O6−z. In the ZnO–CoOz system, Zn substitutes in the tetrahedral Co site of Co3O4 to the maximum amount of (Co2.49Zn0.51)O4−z and Co substitutes in the Zn site of ZnO to (Zn0.94Co0.06)O. The crystal structures of (Co2.7Zn0.3)O4−z, (Zn0.94Co0.06)O, and Ca3(Co1.95 Zn0.05)O6−z are described. Despite the Ca3(Co, Zn)2O6−z series having reasonably high Seebeck coefficients and relatively low thermal conductivity, the electrical resistivity values of its members are too high to achieve high figure of merit, ZT.