Anion Size Effect of Ionic Liquids in Tuning the Thermoelectric and Mechanical Properties of PEDOT:PSS Films through a Counterion Exchange Strategy

Poly(3,4-ethylene dioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) thermoelectric thin films have attracted significant interest due to their solution-processable manufacturing. However, molecular-level tuning or doping is still a challenge to synergistically boost their thermoelectric performance and mechanically stretchable capabilities. In this work, we report a counterion exchange between ionic liquid bis(x-fluorosulfonyl) amide lithium (Li:nFSI, n = 1, 3, 5) with different sizes of anions and a PEDOT:PSS-induced bipolaron network, which significantly boosted the thermoelectric power factor from 0.8 to 157 μW m K-2 at 235 °C and the maximum tensile strain from 3% to over 30%. The π-π* stacking of the PEDOT polymer chains was fine-tuned by the hydrophobic anions of nFSI-, providing a technical route for constructing a bipolaron network and inducing the transition from hopping transport to band-like transport. Furthermore, we found that the stretchable capabilities, that is, εmax, were connected to the gelation time of the PEDOT:PSS-Li:nFSI aqueous solution. Thus, more fluorine-containing groups resulted in longer gelation times and higher εmax values, which significantly improved the processability of the solution-derived films.