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

• Published in: Macromolecular chemistry and physics 2018-05, Vol.219 (9), p.n/a
• Main Authors: Cheng, Xiang‐Le, Zhang, Yun‐Fei, Wu, Yan‐Guang, Fu, Ping, Lin, Zhi‐Dong, Du, Fei‐Peng, Cheng, Chun
• Format: Article
• Language: English
• Subjects: Aniline; aniline oligomers; Block copolymers; n‐type; Oligomers; Polyethylene glycol; Raman spectra; Seebeck effect; Segments; Strong interactions (field theory); Temperature dependence; Temperature sensors; Thermoelectric generators; Thermoelectric materials; thermoelectric properties; triblock copolymers
• ISSN: 1022-1352; 1521-3935
• DOI: 10.1002/macp.201700635

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)n‐b‐PEO‐b‐(ANI)n) (n = 4, 8, 16) are prepared and studied. The results indicate that the (ANI)n‐b‐PEO‐b‐(ANI)n 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 Tg of the (ANI)n‐b‐PEO‐b‐(ANI)n is lower than 300 K, indicating that PEO segments of the (ANI)n‐b‐PEO‐b‐(ANI)n 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)n‐b‐PEO‐b‐(ANI)n 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. A series of temperature‐sensitive and p–n switching aniline oligomer‐block‐polyethylene glycol‐block‐aniline oligomer (ANI)n‐b‐PEO‐b‐(ANI)n thermoelectric materials are prepared via changing the length of the ANI unit. This offers a direction to explore new n‐type organic semiconductors with high negative Seebeck coefficient and optimize the thermoelectric properties of (ANI)n‐b‐PEO‐b‐(ANI)n via modulating the unit number of PEO and aniline oligomers segments.