Ambipolar redox-active polymers with a reversible charging
and discharging capability were synthesized via ring-opening metathesis
polymerization (ROMP) of nitronyl nitroxide radical (NN) mono- and
disubstituted norbornenes which exhibited p- and n-type redox processes
(i.e., one-electron oxidation and reduction per NN group, respectively),
using Grubbs catalyst to avoid side reactions of the radical moiety
allowing over 95% of radicals to survive after ROMP. ROMP of the NN
monomers was accomplished with well-controlled molecular weights of
the resulting NN polymers which were coincident with theoretical values
in the ratio of [monomer]/[catalyst] = 25–200, narrow polydispersity
index (ca. 1.2), and high yields even with [monomer]/[catalyst] >
600. The living character for the ROMP of the NN monomers also allowed
block copolymerization. NN-containing block copolymers were synthesized
through sequential ROMP with benzyl ether-containing norbornene in
high yields. The NN polymer/carbon composite electrode exhibited both
p- and n-type charging/discharging with plateau potentials near the
redox potentials of the polymer at 0.78 and −0.80 V vs Ag/AgCl,
respectively. The spin-coated layer electrode of the NN polymer immobilized
on a current collector also demonstrated a fast charging/discharging
performance in the range of 10–100 C rates and a cycle stability
especially for the p-type reaction. These results made the NN polymer
accessible as ambipolar electrode-active materials and also encouraged
other organic radicals to be candidates for electroactive polymers.
Poly(norbornene)-g-poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl)
(PNB-g-PTMA) was prepared by a grafting-through approach
based on anionic polymerization of 4-methacryloyloxy-2,2,6,6-tetramethylpiperidin-1-oxyl
using a norbornene-substituted diphenylhexyllithium to yield a norbornene-functionalized
macromonomer (NB-PTMA) and subsequent ring-opening metathesis polymerization
of NB-PTMA using a Grubbs third-generation catalyst, which avoided
critical side reactions involving the nitroxide radical of TEMPO moiety.
The anionic polymerization resulted in high yields (>94%), narrow
polydispersity indices (<1.20), and radical concentrations (0.95
radicals per monomer unit). The ROMP also resulted in high yields
(>98%) and high radical concentrations (0.95 radicals per monomer
unit), by virtue of the functional group tolerance of these reactions.
Single molecular dimension of PNB-g-PTMA was measured
by dynamic light scattering and by atomic force microscopy (AFM),
which precisely reflected the bottlebrush structure to reveal the
presence of the TEMPO group crowded at the periphery of the molecule.
The lengths of PNB-g-PTMA along the macromolecular
side chains and the polynorbornene main chain were both approximately
equal to the theoretical lengths estimated by the degree of polymerization
for each chain. The number-average diameter of PNB-g-PTMA in THF increased with initial NB-PTMA ratio to the Grubbs catalyst.
Photo-cross-linked thin layer electrodes of PNB-g-PTMA demonstrated the reversible redox reaction at 0.80 V vs Ag/AgCl
corresponding to the TEMPO/TEMPO+ couple and quantitative
charging/discharging processes even at 120 C rate (i.e., full charging
in 30 s). As a novel application of redox-active polymers, PNB-g-PTMA exhibited 95% efficiency of the theoretical charge
capacity in a flow cell system, based on the unique properties of
bottlebrush polymers such as the defined molecular dimension and relatively
low solution viscosity in comparison with corresponding linear polymers.
Anionic polymerization of 4-methacryloyloxy-TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidin-1-oxyl) was successfully carried out using methyl methacrylate-capped 1,1-diphenylhexyllithium (DPHLi/MMA), of which nucleophilicity is moderate enough to suppress the side reaction between the nitroxide radical of TEMPO moiety and the carbanion of DPHLi, to yield the radical polymer with well-controlled molecular weight, narrow polydispersity index (PDI < 1.10), high yield (>95%), and almost 1.0 radicals per monomer unit.
A fast and reversible charge storage capability was established for the radical polyether/SWCNT composite layer with a large layer thickness of several tens of micrometres despite the low SWCNT content of 10%.
An electrode-attached layer of poly(phenylacetylene) bearing a pendant nitronyl nitroxide group per repeating unit, obtained by the Rh-catalyzed polymerization of 2-(4-ethynylphenyl)-4,4,5,5-tetramethylimidazoline-l-oxyl 3-oxide, underwent oxidation and reduction at 0.80 and −0.84 V vs. Ag/AgCl, respectively. The magnetically determined unpaired electron density of 92% was coulometrically reproduced, which supported the presumption that the radical survived during the course of the polymerization to allow both positive and negative charging of the pristine neutral polymer substantially per repeating unit. Galvanostatic Coulomb titration revealed the charge storage capability of the polymer, which demonstrated usefulness as organic electrode-active material with unprecedented ambipolar chargeability.
A couple of totally reversible redox-active molecules, which are different in redox potentials, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) and viologen (V(2+)), were employed to give rise to a rectified redox conduction effect. Single-layer and bilayer devices were fabricated using polymers containing these sites as pendant groups per repeating unit. The devices were obtained by sandwiching the redox polymer layer(s) with indium tin oxide (ITO)/glass and Pt foil electrodes. Electrochemical measurements of the single-layer device composed of polynorbornene-bearing TEMPO (PTNB) exhibited a diffusion-limited current-voltage response based on the TEMPO(+)/TEMPO exchange reaction, which was almost equivalent to a redox gradient through the PTNB layer depending upon the thickness. The bilayer device gave rise to the current rectification because of the thermodynamically favored cross-reaction between TEMPO(+) and V(+) at the polymer/polymer interface. A current-voltage response obtained for the bilayer device demonstrated a two-step diffusion-limited current behavior as a result of the concurrent V(2+)/V(+) and V(+)/V(0) exchange reactions according to the voltage and suggested that the charge transport process through the device was most likely to be rate-determined by a redox gradient in the polymer layer. Current collection experiments revealed a charge transport balance throughout the device, as a result of the electrochemical stability and robustness of the polymers in both redox states.
Summary: A nitroxide radical-substituted polyether, poly(TEMPO-substituted glycidyl ether) (PTGE), was synthesized using a potassium tert-butoxide/18-crown-6 initiator. The presence of 18-crown-6 effected significant improvement in the reactivity of the chain end, thus allowing the polymerization to proceed at moderate temperatures to suppress the deactivation of the pendant nitroxide group. A high molecular-weight polyether with a theoretical radical concentration was first obtained in high yield. Charging and discharging cyclability was much improved by cross-linking, which helped the electrode-active material stay on a current collector during the electrolysis. The polymer/vapor-grown carbon nanofiber composite electrode exhibited a redox capacity comparable to the formula weightbased theoretical density over 10 3 cycles and fast charging/discharging capability up to a rate of 60 C which corresponded to full charging and discharging in 60 s. The redox capacity was almost maintained for a composite layer with a remarkably high polymer ratio of 90 %, which demonstrated the presence of effective percolation network of the carbon nanofiber due likely to the affinity of the polyether to the carbon material.
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