Thermally Sensitive N‐Type Thermoelectric Aniline Oligomer‐Block‐Polyethylene Glycol‐Block‐Aniline Oligomer ABA Triblock Copolymers.

Abstract: High‐performance n‐type thermoelectric polymers are vital in the development of polymer thermoelectric generators (PTEGs). However, the progress is very slow due to their low stability and low thermoelectric properties. Here, aniline oligomer‐block‐polyethylene glycol‐block‐aniline oligomer (ANI)<italic>n</italic>‐b‐PEO‐b‐(ANI)<italic>n</italic>) (<italic>n</italic> = 4, 8, 16) are prepared and studied. The results indicate that the (ANI)<italic>n</italic>‐b‐PEO‐b‐(ANI)<italic>n</italic> show unique temperature sensitivity and switch from p‐type to n‐type when the temperature is above 300 K. Differential scanning calorimetry curves show that the <italic>T</italic>g of the (ANI)<italic>n</italic>‐b‐PEO‐b‐(ANI)<italic>n</italic> is lower than 300 K, indicating that PEO segments of the (ANI)<italic>n</italic>‐b‐PEO‐b‐(ANI)<italic>n</italic> easily move above 300 K and have high flexibility. Temperature‐dependent Raman spectra confirm that there are strong interactions between PEO segments and aniline oligomers during the raising temperature, and PEO chains might provide plenty of negative charge at high temperature, which can convert the (ANI)<italic>n</italic>‐b‐PEO‐b‐(ANI)<italic>n</italic> into n‐type thermoelectric materials. To adjust the number of aniline unit, (ANI)8‐b‐PEO‐b‐(ANI)8 shows excellent n‐type characteristics with Seebeck coefficient as large as −1171 µV K−1 at 381 K. The strong interaction between PEO and aniline oligomers plays a dominant role in the n‐type thermoelectric performance of the triblock copolymers, which have potential application in the field of PTEGs and temperature sensors. [ABSTRACT FROM AUTHOR]