Electropolymerized Star-Shaped Benzotrithiophenes Yield π-Conjugated Hierarchical Networks with High Areal...

High-surface-area π-conjugated polymeric networks have the potential to lend outstanding capacitance to supercapacitors because of the pronounced faradaic processes that take place across the dense intimate interface between active material and electrolytes. In this report, we describe how benzo[1,2-b:3,4-b':5,6-b″]trithiophene (BTT) and tris(ethylenedioxythiophene)benzo[1,2-b:3,4-b':5,6-b″]trithiophene (TEBTT) can serve as 2D (trivalent) building blocks in the development of electropolymerized hierarchical π-conjugated frameworks with particularly high areal capacitance. In comparing electropolymerized networks of BTT, TEBTT, and their copolymers with EDOT, we show that TEBTT/EDOT-based copolymers, i.e., P(TEBTT/EDOT), can achieve higher areal capacitance (e.g., as high as 443.8 mF cm(-2) at 1 mA cm(-2)) than those achieved by their respective homopolymers (PTEBTT and PEDOT) in the same experimental conditions of electrodeposition (PTEBTT: 271.1 mF cm(-2) (at 1 mA cm(-2)) and

12.1 mF cm(-2) (at 1 mA cm(-2))). For example, P(TEBTT/EDOT)-based frameworks synthesized in a 1:1 monomer-to-comonomer ratio show a ca. 35× capacitance improvement over PEDOT. The high areal capacitance measured for P(TEBTT/EDOT)-based frameworks can be explained by the open, highly porous hierarchical morphologies formed during the electropolymerization step. With >70% capacitance retention over 1000 cycles (up to 89% achieved), both PTEBTT- and P(TEBTT/EDOT)-based frameworks are resilient to repeated electrochemical cycling and can be considered promising systems for high life cycle capacitive electrode applications.