Redox equilibrium of a zwitterionic radical polymer in a non-aqueous electrolyte as a novel Li+ host material in a Li-ion battery

Effect of intrachain sulfonic acid dopants on the solid-state charge mobility of a model radical polymer

“…The procedure for the synthesis of PTMA-co-PVS was modified here relative to previous reports [35,36]. Specifically, the sodium salt form (VS-Na) of the monomer was polymerized instead of the more acidic vinylsulfonic acid (VSA) monomer; this is because the latter of these requires a neutralization step to improve the solubility of the copolymer.…”

“…Poly(2,2,6,6-tetramethyl-4-piperidyl methacrylate)-co-poly(vinylsulfonic acid sodium salt) (PTMPM-co-PVS) was synthesized via a free radical polymerization mechanism in a manner similar to previous reports [35,36]. The following is a brief example of the polymerization process.…”

“…Here, we extend this paradigm to the realm of radical polymers through the intentional addition of ion-bearing repeat units to the macromolecular architecture of PTMA; these ion-bearing repeat units serve as intramolecular dopants in order to enhance the transport ability of the copolymers relative to pristine PTMA. Specifically, we have synthesized a series of copolymers containing both PTMA and an ionic molecular dopant, poly(vinylsulfonic acid sodium salt) (PVS), using a free radical polymerization mechanism to yield poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate)-copoly(vinylsulfonic acid sodium salt) (PTMA-co-PVS) [35,36]. After confirming the macromolecular architectures of the radical polymerbased copolymers using established spectroscopic techniques, the space charge-limited hole mobility values of the copolymers were established and found to be~10 −5 cm 2 V −1 s −1 in optimized conditions and dependent on the level of intramolecular dopants.…”

Porous Carbons – Hyperbranched Polymers – Polymer Solvation

“…Nitroxide-based polymers and their modified electrodes have been discussed as efficient components for battery applications (e.g., [10,124,[533][534][535][536][537]). These polymers can even be used as active surfaces for electrochemical writing on the nanoscale using a current-sensing atomic force microscope [538].…”

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

“…1-5 When the redox-active sites are electrochemically reversible [6][7][8][9] and are bound to a polymer chain, an electron self-exchange reaction between the neighboring sites effects the redox mediation through the polymer layer, which requires that electroneutralization by electrolyte ions is accomplished throughout the layer to maintain the electroactivity. [10][11][12] Aliphatic, or non-conjugated polymers populated with organic robust radicals such as nitroxide, [13][14][15][16][17][18][19][20][21][22][23] nitronyl nitroxide, 24,25 spirobisnitroxide 26 and galvinoxyl 27,28 have been found to be the typical examples, and their ideal redox-mediating properties 29 are different from those of conventional redox polymers such as poly (vinylferrocene), [30][31][32][33] which has been dominated by the 'break-in effect' of the electroneutralizing ions to give rise to limited charge capacity and hysteresis during the charging/discharging process. The ideal, that is, diffusion-limited behavior by the so-called 'radical polymers' 34,35 has led to reversible and exhaustive charging with the simple redox diffusive process formulated by the finite diffusion equation 36 for the layer with a discrete thickness on a current collector, 37 and by the equation for semi-infinite diffusion 36 that applies to wholly gelated cells with the radical polymer.…”