Nanostructured calcium cobalt oxide Ca3Co4O9 as thermoelectric material. Effect of nanostructure on local coordination, Co charge state and thermoelectric properties

摘要

The preparation of pure Ca3Co4O9 materials in the form of dense bodies made of nano-sized grains was investigated by combining a sol-gel route, different thermal cycles, a ball-milling post-treatment and final densification with HP-FAST (High Pressure-Field Assisted Sintering). We found that an effective way for obtaining nano-sized compact bodies with only a marginal increase of the particle sizes of the original powder was the operation of HP-FAST at extremely high pressures (up to 430 MPa) and comparatively low temperatures. A ball-milling treatment before HP-FAST compaction was then required to hinder the large plastic deformation occurring when using these pressures. In contrast, un-milled powders could be densified by HP-FAST only at lower pressure and therefore required higher temperatures, thus losing their nanostructure.