Mesoscale Radical Polymers: Bottom‐Up Fabrication of Electrodes in Organic Polymer Batteries

Oyaizu, Kenichi; Nishide, Hiroyuki

doi:10.1002/9783527628940.ch9

Cited by 4 publications

(3 citation statements)

References 64 publications

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“…This paper’s main topic is limited to redox-active species that are robust in the radical states, which are generally considered as “persistent radicals” (Class I-a). Representative compounds are nitroxides, phenolic radicals, verdazyls, Blatter radicals, and triallylaminiums, Scheme . , The units are often introduced as side or main chains of macromolecules in radical polymers. ,,− …”

Section: Introductionmentioning

confidence: 99%

Redox: Organic Robust Radicals and Their Polymers for Energy Conversion/Storage Devices

Hatakeyama-Sato,

Oyaizu

2023

Chem. Rev.

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Persistent radicals can hold their unpaired electrons even under conditions where they accumulate, leading to the unique characteristics of radical ensembles with open-shell structures and their molecular properties, such as magneticity, radical trapping, catalysis, charge storage, and electrical conductivity. The molecules also display fast, reversible redox reactions, which have attracted particular attention for energy conversion and storage devices. This paper reviews the electrochemical aspects of persistent radicals and the corresponding macromolecules, radical polymers. Radical structures and their redox reactions are introduced, focusing on redox potentials, bistability, and kinetic constants for electrode reactions and electron self-exchange reactions. Unique charge transport and storage properties are also observed with the accumulated form of redox sites in radical polymers. The radical molecules have potential electrochemical applications, including in rechargeable batteries, redox flow cells, photovoltaics, diodes, and transistors, and in catalysts, which are reviewed in the last part of this paper.

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Section: Introductionmentioning

confidence: 99%

Redox: Organic Robust Radicals and Their Polymers for Energy Conversion/Storage Devices

Hatakeyama-Sato,

Oyaizu

2023

Chem. Rev.

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“…Organic batteries that permit the use of less resistive porous separators, like those of Li-ion batteries, have been developed by using particular polymers which survive on the current collector and yet maintain their activity as a result of enhanced exchange reaction between highly populated redox-active sites bound to aliphatic main chains. − In fact, molecular design of organic electrodes from the viewpoints of the mass- and electron-transfer processes is essential to improve the performance of the organic battery . We anticipated that polymers should also help to replace the porous separator for ion-exchange membranes that are currently employed to fractionate the electroactive fluids in flow batteries, especially when the electroactive polymers possess discrete molecular sizes in a mesoscale . Here we report the synthesis of a redox-active bottlebrush polymer characterized by an expanded dimensionality from those of linear analogues and the excellent charge storage capability accomplished by the polymer solution, with potential application to the flow battery applications …”

Section: Introductionmentioning

confidence: 99%

Expanding the Dimensionality of Polymers Populated with Organic Robust Radicals toward Flow Cell Application: Synthesis of TEMPO-Crowded Bottlebrush Polymers Using Anionic Polymerization and ROMP

et al. 2014

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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.

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“…This is the first example detecting the interaction between localized spins and conducting electrons in an organic molecular assembly, i.e., a molecule-based spintronics using not only the charge but also the spin of an electron (Sugawara et al, 2011). Meanwhile, for the last decade the redox properties of NRs have been utilized for the development of environmentally benign organic cathode-active materials for rechargeable batteries with a high energy-density, such as a stable nitroxide polyradical, poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate (4) (Figure 1) (Nakahara, 2002;Oyaizu & Nishide, 2010;Suga & Nishide, 2010). Thus, stable NR structures have been used as the spin source or the redox species to develop metal-free solid-state magnetic materials and spintronic devices, or polymer battery devices, respectively.…”

Section: Introductionmentioning

confidence: 99%

Magnetic and Electric Properties of Organic Nitroxide Radical Liquid Crystals and Ionic Liquids

Tamura¹,

Uchida²,

Suzuki³

2012

Nitroxides - Theory, Experiment and Applications

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Mesoscale Radical Polymers: Bottom‐Up Fabrication of Electrodes in Organic Polymer Batteries

Cited by 4 publications

References 64 publications

Redox: Organic Robust Radicals and Their Polymers for Energy Conversion/Storage Devices

Redox: Organic Robust Radicals and Their Polymers for Energy Conversion/Storage Devices

Expanding the Dimensionality of Polymers Populated with Organic Robust Radicals toward Flow Cell Application: Synthesis of TEMPO-Crowded Bottlebrush Polymers Using Anionic Polymerization and ROMP

Magnetic and Electric Properties of Organic Nitroxide Radical Liquid Crystals and Ionic Liquids

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