Functionalization of Polypyrrole Nanopipes with Redox‐Active Polyoxometalates for High Energy Density Supercapacitors

Hybrid materials are very attractive for the fabrication of high‐performance supercapacitors. Here, we have explored organic–inorganic hybrid materials based on open‐end porous 1 D polypyrrole nanopipes (PPy‐NPipes) and heteropolyoxometalates (phosphotungstate ([PW12O40]3−, PW12) or phosphomolybdate ([PMo12O40]3−, PMo12)) that display excellent areal capacitances. Two different hybrid materials (PMo12@PPy and PW12@PPy) were effectively synthesized and used for symmetric supercapacitors. The anchoring of the inorganic nanoclusters onto the conducting polymer nanopipes led to electrodes that stood up to our best expectations exhibiting outstanding areal capacitances that are almost 1.5 to 2 fold higher than that of pristine PPy‐NPipes. In addition, symmetric cells based on PMo12@PPy and PW12@PPy hybrid electrodes were fabricated and showed significant improvement in cell performance with very high volumetric capacitances in the range of 6.3–6.8 F cm−3 (considering the volume of whole device). Indeed, they provide extended potential windows in acidic electrolytes (up to 1.5 V) which led to ultrahigh energy densities of 1.5 and 2.2 mWh cm−3 for PMo12@PPy and PW12@PPy cells, respectively. Thus, these unique organic‐inorganic hybrid symmetric cells displayed extraordinary electrochemical performances far exceeding those of more complex asymmetric systems. POM‐Nanopipes: Redox‐active polyoxometalates (POMs) are used to functionalize polypyrrole nanopipes and obtain hybrid organic–inorganic materials (PMo12@PPy and PW12@PPy) with very high volumetric capacitances that can be used in supercapacitors.