Abnormally enhanced thermoelectric transport properties of SWNT/PANI hybrid films by the strengthened PANI molecular ordering

Single-walled carbon nanotube (SWNT)/polyaniline (PANI) hybrid films were prepared by casting the suspension containing well-dispersed SWNTs and CSA-doped PANI. The electrical conductivity of the SWNT/PANI film at first increased with the increasing SWNT content and then decreased at high SWNT content, whereas the Seebeck coefficient increased monotonically in the present SWNT content range. Moreover, the electrical conductivity values of the SWNT/PANI composites were much higher than the values calculated based on the series-connected two-component mixture model, whereas the dependence of the Seebeck coefficient on the SWNT content fitted well with the mixture model. Thermal conductivities increased with the SWNT content, but the rate of increase was much lower than the values estimated using the mixture model. The maximum values of electrical conductivity and Seebeck coefficient of hybrid films were up to 769 S cm−1 and 65 μV K−1. Consequently, the maximum thermoelectric power factor and ZT value at room temperature reached 176 μW m−1 K−2 and 0.12, respectively. The optimal TE property of the SWNT/PANI hybrid film was remarkably higher than those of either individual component of the composite, and exhibits the highest values for inorganic–organic composite materials reported so far. XRD and Raman analyses revealed that the PANI molecules in the composite film had a more expanded conformation, and were more orderly arranged compared with both pure PANI bulk and pure PANI film. The abnormally enhanced thermoelectric performance is attributed to the highly ordered PANI interface layer on the SWNT surface, which formed by the synergetic effect of chain expansion by the chemical interactions between PANI and the solvent and chain-ordering due to the π–π conjugation between PANI and CNTs.