Facile charge transport and storage by a TEMPO-populated redox mediating polymer integrated with polyaniline as electrical conducting path

Abstract

A copolymer of TEMPO-and aniline-substituted norbornene was prepared by ring-opening metathesis polymerization of the corresponding monomers. Electropolymerization of the pendant aniline groups in the copolymer gave a layer of polynorbornene populated with the redox-active TEMPO pendants, in which polyaniline chain was incorporated. Electroactivity of the TEMPO pendants throughout the layer and its excellent charging/discharging cyclability, in addition to the amorphous nature of the layer, suggested that the polyaniline chain was homogeneously dispersed in the layer and that each chain served as crosslinking moiety. The effect of the polyaniline chains was further enhanced when they were formed by in-situ electropolymerization of the aniline group in the preformed layer of the copolymer/polyaniline composite. The polyaniline chain served as a conducting path to reduce the charge-transfer resistance for redox mediation, which gave rise to an excellent rate performance for the charging/ discharging process of the layer, compared with those for the composite layers of TEMPO-substituted polymers with polyaniline and other conductive additives prepared by the conventional grinding methods.

Engineering radical polymer electrodes for electrochemical energy storage

“…Rather than mixing in conductive additive, conductive pathways may be built into the polymer via chemical design: electropolymerization and copolymerization of conducting polymers [112,191]. Electropolymerization and electrochemical deposition of conducting polymers can provide improved electronic connections within the electrode with the possibility of self-limiting polymerization (i.e., a coating that is naturally formed at the optimal thickness) [27,118,168,191,192].…”

“…While conducting polymers have been used as conductive additives for LiFePO 4 electrodes [27,115,116], polymer-based electrodes allow additional designs via copolymerization of radical polymers and conducting polymers [193]. Several recent studies show the effectiveness of this method [11,28,151,191,194,195]. Specifically, Oyaizu et al co-polymerized poly(aniline) and poly(TEMPO-norbornene), and the electrode provides a flat discharge curve even at high discharge rates (10-40 C-rate) [191].…”

Nanopatterning of Stable Radical Containing Block Copolymers for Highly Ordered Functional Nanomeshes

“…In order to combine the redox activity of such polymers with other material properties, new copolymers were developed. 13 Block copolymers with a stable radical block and another functional block could, in the case of long-range ordered self-assembly, lead to patterned nitroxide groups on a surface. Self-assembly of block copolymers, however, is hindered if polymer chain length is ill-defined or shorter than a composition and interaction parameter dependent value.…”

Redox mediation at poly(o-aminophenol) coated electrodes: mechanistic diagnosis from steady state polarization curves

“…Redox mediation has attracted the attention of many researchers [4][5][6][7][8][9][10][11][12][13][14][15], mainly because the possibility of tuning the electrochemical reactivity of the coated electrode towards a specific end, both by choosing appropriate redox mediators and by controlling the film characteristics. It is also possible to design mediators with certain specific properties, such as ion selectivity, conductivity, formal potential, etc.…”