All-Oxide Thermoelectric Module with in Situ Formed Non-Rectifying Complex p–p–n Junction and Transverse Thermoelectric Effect

All-oxide thermoelectric modules for energy harvesting are attractive because of high-temperature stability, low cost, and the potential to use nonscarce and nontoxic elements. Thermoelectric modules are mostly fabricated in the conventional π-design, associated with the challenge of unstable metallic interconnects at high temperature. Here, we report on a novel approach for fabrication of a thermoelectric module with an in situ formed p-p-n junction made of state-of-the-art oxides Ca 3 Co 4- x O 9+δ (p-type) and CaMnO 3 -CaMn 2 O 4 composite (n-type). The module was fabricated by spark plasma co-sintering of p- and n-type powders partly separated by insulating LaAlO 3 . Where the n- and p-type materials originally were in contact, a layer of p-type Ca 3 CoMnO 6 was formed in situ. The hence formed p-p-n junction exhibited Ohmic behavior and a transverse thermoelectric effect, boosting the open-circuit voltage of the module. The performance of the module was characterized at 700-900 °C, with the highest power output of 5.7 mW (around 23 mW/cm 2 ) at 900 °C and a temperature difference of 160 K. The thermoelectric properties of the p- and n-type materials were measured in the temperature range 100-900 °C, where the highest zT of 0.39 and 0.05 were obtained at 700 and 800 °C, respectively, for Ca 3 Co 4- x O 9+δ and the CaMnO 3 -CaMn 2 O 4 composite.