Electrochemically Nanostructured Polyvinylferrocene/Polypyrrole Hybrids with Synergy for Energy Storage

Abstract

Unconjugated redox polymers, such as polyvinylferrocene (PVF), have rarely been used for energy storage due to their low intrinsic conductivity. Conducting polymers with conjugated backbones, though conductive, may suffer from insuffi cient exposure to the electrolyte due to the often formed nonporous structures. The present work overcomes this limitation via simultaneous electropolymerization of pyrrole and electroprecipitation of PVF on electrode surfaces. This synthesis method relies on the π-π stacking interactions between the aromatic pyrrole monomers and the metallocene moieties of PVF. This fabrication process results in a highly porous polymer fi lm, which enhances the ion accessibility to polypyrrole (PPy). PPy serves as a "molecular wire," improving the electronic conductivity of the hybrid and the utilization effi ciency of ferrocene. The PVF/PPy hybrid exhibited a specifi c capacitance of 514.1 F g −1 , which signifi cantly exceeds those of PPy (27.3 F g −1 ) and PVF (79.0 F g −1 ), respectively. This approach offers an alternative to nanocarbon materials for improving the electronic conductivity of polymer hybrids, and suggests a new strategy for fabricating nanostructured polymer hybrids. This strategy can potentially be applied to various polymers with π-conjugated backbones and redox polymers with metallocene moieties for applications such as energy storage, sensing, and catalysis.

Energetically efficient electrochemically tunable affinity separation using multicomponent polymeric nanostructures for water treatment

“…27 The enhanced adsorption capabilities enabled a higher degree of separation during an ETAS operation. Second, incorporation of a conductive CNT core affected the electrochemical behavior of the key molecule with redox-tunable hydrophobicity (i.e., ferrocene), resulting in enhanced energetic efficiencies.…”

“…2a) consisted of a carbon cloth (CC) with a conformal coating of a polyvinylferrocene/polypyrrole (PVF/PPY) hybrid, fabricated via simultaneous electro-polymerization of pyrrole and electrodeposition of PVF. 27 In the binary polymer film, the ferrocene moieties in PVF rendered redox-tunable hydrophobicity (i.e., the oxidized ferrocene is significantly more hydrophilic than its reduced form), 28 while the conjugated PPY chains established electron transport pathways to permit electrical control. The CC, composed of bendable carbon microfibers, served as a flexible and robust conductive substrate.…”

“…4a) was composed of a metallic carbon nanotube (CNT) core with a conformal coating of PVF/PPY, formed by the non-covalent p stacking interaction between the three components. 27,34 Hereafter the ternary nanostructure is denoted PVF/PPY/CNT. To construct ETAS adsorbents, we immobilized PVF/PPY/CNT onto the CC substrate by electrochemical deposition (Experimental).…”

“…Cyclic voltammetric (CV) scans at 0.1 V s À1 between 0.0 and 0.8 V showed that PVF/PPY could be oxidized and reduced for 300 cycles with negligible loss of the current signal (o1% decrease in the integrated CV area), indicating good electrochemical stability of the hybrid during the cyclic operation. For further enhancement of the performance stability of ETAS adsorbents, several previously developed methods such hydrothermal treatment 27 or organic vapor deposition 32 could be employed. Also, our control experiments show that application of an oxidative potential (0.6 V) did not result in degradation of SOG (Fig.…”

Ionothermally synthesized hierarchical porous Schiff-base-type polymeric networks with ultrahigh specific surface area for supercapacitors

“…For instance, the nitrogen doping will improve the wettability of carbonaceous materials and provide more active sites for the ion accumulation in the electrode materials. 5,6 Many efforts have been done to increase the effective surface area while adjusting the pore distribution, 7,8 to introduce heteroatoms into the carbon skeleton 9,10 and to develop new materials with new modalities.…”