Nanostructured polypyrrole: enhancement in thermoelectric figure of merit through suppression of thermal conductivity

Semi-crystalline polypyrrole (PPy) nanotubes were synthesized through a chemical polymerization route using methyl orange-ferric chloride (MO-FeCl₃) as a template for growth. The thermoelectric properties of these PPy nanotubes have been studied in the temperature range 300–380 K after treatment with various dopants such as hydrochloric acid (HCl), p-toluene-sulphonic acid monohydrate (ToS), and tetrabutyl ammonium hexaflurophosphate (PF6). It has been observed that these dopants affect the electrical and thermal transport properties of PPy nanotubes in different ways. The temperature dependence of electrical resistivity suggests that pure PPy and ToS-doped PPy nanotubes exhibit a critical regime of metal-to-insulator transition, and doping with HCl drives them into the metallic regime. In contrast, PF6 doping of PPy nanotubes carries them into the insulating regime and these samples exhibited the highest figure of merit of ∼3.4  ×  10^‒3 at 380 K, which was 240% higher than the value obtained in the case of pristine PPy nanotubes. Strongly repressed thermal conductivity along with moderately high Seebeck coefficient and electrical conductivity have been found to be responsible for the high figure of merit observed in PF6-doped PPy nanotubes. The suppression of thermal conductivity in PF6-doped PPy nanotubes is attributed to the scattering of the spectrum of phonons via hierarchical length-scale defect structures present in the sample. (paper)