Synthesis and thin-film self-assembly of radical-containing diblock copolymers

Rostro, Lizbeth; Baradwaj, Aditya G.; Muller, Alexander R.; Laster, Jennifer S.; Boudouris, Bryan W.

doi:10.1557/mrc.2015.27

Cited by 11 publications

(9 citation statements)

References 31 publications

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“…37 We previously reported the formation of electrochemically active micelles with a polystyrene (PS) insoluble core and PTMA soluble coronal chains using PTMA-b-PS diblock copolymers dissolved in commonly used Li-ion battery electrolytes. 39 In 2014, Nishide and Suga reported the synthesis of pendant radicaland ion-containing block copolymers. 39 In 2014, Nishide and Suga reported the synthesis of pendant radicaland ion-containing block copolymers.…”

Section: Introductionmentioning

confidence: 99%

“…38 For self-assembly in thin lms, Boudouris et al reported the possibility to form thin lms with tailored morphologies from polydimethylsiloxane-block-PTMA (PDMS-b-PTMA) diblock copolymers using solvent vapour annealing in CHCl 3 . 39 In 2014, Nishide and Suga reported the synthesis of pendant radical-and ion-containing block copolymers. The self-assembled thin lms exhibit different morphologies from spheres to inverse spheres and were used as an active layer in a diode-structured thin-lm device, combining the redox-active radicals of one block to the charge-compensating ions of the other one.…”

Section: Introductionmentioning

confidence: 99%

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Nanostructured organic radical cathodes from self-assembled nitroxide-containing block copolymer thin films

et al. 2015

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This contribution describes the formation of nanostructured thin film organic radical cathodes. First, the self-assembly of poly(styrene)-block-poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA-b-PS) diblock copolymers is detailed. In order to improve the nano-morphology of the immiscible PTMA and PS domains, the effect of thermal and solvent annealing is investigated. The formation of thin films with different morphologies such as cylindrical or lamellar nanostructures is observed depending on the processing conditions. The electrochemical properties of the nanostructured films are further investigated to assess the redox activity of the PTMA domains. Cyclic voltammetry of PTMA-b-PS diblock copolymers, either in dissolved or thin film supported configuration, confirms the reversible redox behavior of the nitroxide radical. Galvanostatic cycling of the thin film nanostructured cathodes reveals good capacity retention with fast charge/discharge response resulting from efficient charge and ion transfer as well as structural integrity. Such nanostructured organic radical cathodes provide opportunities for the fabrication of new generation nanostructured organic radical battery architectures.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nanostructured organic radical cathodes from self-assembled nitroxide-containing block copolymer thin films

et al. 2015

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“…Therefore, electrolyte‐supported radical polymer systems have extremely useful transport properties, as the liquid‐based electrolytes provide ample mobility to the radical polymer pendant groups. On the other hand, only recently was it established that these types of reactions can also occur in a rather rapid manner in solid‐state organic electronic applications . Specifically, the model radical polymer, poly(2,2,6,6‐tetramethylpiperidinyloxy methacrylate) (PTMA), is an extraordinarily transparent material and can be easily synthesized in large batches .…”

Section: Introductionmentioning

confidence: 99%

On the Environmental and Electrical Bias Stability of Radical Polymer Conductors in the Solid State

Baradwaj

Rostro

Boudouris

2015

Macro Chemistry & Physics

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Radical polymers are emerging as a promising class of electronically active macromolecules for solid‐state organic electronic applications due to their synthetic flexibility and scalability; however, the electrical and chemical stability of radical polymer thin films has yet to be established. Here, it is demonstrated that the model radical polymer, poly(2,2,6,6‐tetramethylpiperidinyloxy methacrylate) (PTMA), shows excellent solid‐state electrochemical stability when exposed to both bias stressing and varying amounts of moisture in the environment. Specifically, PTMA thin films show consistent performance when continuously swept across a variety of voltage ranges. Furthermore, PTMA remains stable when exposed to a constantly applied bias for 20 h. These two key results demonstrate the stability of the open‐shell repeat unit and the reversibility of the chemical oxidation–reduction (redox) reaction that facilitates charge transport. Additionally, PTMA thin films that are exposed to a range of relative humidity values for 2 h retained consistent electronic performance before and after humidity exposure. This highlights that exposure to water vapor does not decrease the robustness associated with the nitroxide radical. These results establish the stoutness associated with radical polymers and highlight the potential for radical polymers to be implemented in a number of advanced organic electronic technologies.

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“…This allowed for easy visualization of the self‐assembled thin films in the atomic force microscope (AFM). Additionally, our group showed that PTMPM could be grown from bromine‐terminated poly(dimethyl siloxane) (PDMS) to generate poly(dimethyl siloxane)‐ b ‐poly(2,2,6,6‐tetramethylpiperidine‐4‐yl methacrylate) (PDMS‐PTMPM) diblock copolymers . Upon oxidation of the PTMPM moiety to PTMA, the radical polymer‐containing PDMS‐PTMA diblock copolymer was readily obtained.…”

Section: Radical Polymersmentioning

confidence: 99%

Recent advances in the syntheses of radical-containing macromolecules

Wingate

Boudouris

2016

J. Polym. Sci. Part A: Polym. Chem.

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Tailor-made polymers containing specific chemical functionalities have ushered in a number of emerging fields in polymer science. In most of these next-generation applications the focus of the community has centered upon closed-shell macromolecules. Conversely, macromolecules containing stable radical sites have been less studied despite the promise of this evolving class of polymers. In particular, radical-containing macromolecules have shown great potential in magnetic, energy storage, and biomedical applications. Here, the progress regarding the syntheses of open-shell containing polymers are reviewed in two distinct subclasses. In the first, the syntheses of radical polymers (i.e., materials composed of nonconjugated macromolecular backbones and with open-shell units present on the polymer pendant sites) are described. In the second, polyradical (i.e., macromolecules containing stabi-lized radical sites either within the macromolecular backbone or those containing radical sites that are stabilized through a large degree of conjugation) synthetic schemes are presented. Thus, the state-of-the-art in open-shell macromolecular syntheses will be reported and future means by which to advance the current archetype will be discussed. By detailing the synthetic pathways possible for, and the inherent synthetic limitations of, the creation of these functional polymers, the community will be able to extend the bounds of the radical-containing macromolecular paradigm.

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Synthesis and thin-film self-assembly of radical-containing diblock copolymers

Abstract: Abstract

Cited by 11 publications

References 31 publications

Nanostructured organic radical cathodes from self-assembled nitroxide-containing block copolymer thin films

Nanostructured organic radical cathodes from self-assembled nitroxide-containing block copolymer thin films

On the Environmental and Electrical Bias Stability of Radical Polymer Conductors in the Solid State

Recent advances in the syntheses of radical-containing macromolecules

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