Development of High Performance Thermoelectric Polymers via Doping or Dedoping Engineering

Abstract It is of great significance to develop high‐performance thermoelectric (TE) materials, because they can be used to harvest waste heat into electricity and there is abundant waste heat on earth. The conventional TE materials are inorganic semimetals or semiconductors like Bi 2 Te 3 and its derivatives. However, they have problems of high cost, scarce/toxic elements, high thermal conductivity, and poor mechanical flexibility. Organic TE materials emerged as the next‐generation TE materials because of their merits including solution processability, low cost, abundant element, low intrinsic thermal conductivity, and high mechanical flexibility. Organic TE materials are mainly conducting polymers because of their high conductivity. Both the conductivity and Seebeck coefficient depend on the doping level, and they are interdependent. Hence, the TE properties of polymers can be improved through doping/dedoping engineering. There are three types of doping forms, oxidative (or reductive) doping, protonic acid doping, and charge transfer doping. Accordingly, they can be dedoped by different approaches. In this article, we review the methods to dope and dedope p ‐type and n ‐type TE polymers and the combination of doping and dedoping to optimize their TE properties. Secondary doping is also covered, since it can significantly enhance the conductivity of some TE polymers.