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Title: Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers

Abstract

Macromolecular radicals are receiving growing interest as functional materials in energy storage devices and in electronics. With the need for enhanced conductivity, researchers have turned to macromolecular radicals bearing conjugated backbones, but results thus far have yielded conjugated radical polymers that are inferior in comparison to their non-conjugated partners. The emerging explanation is that the radical unit and the conjugated backbone (both being redox active) transfer electrons between each other, essentially “quenching” conductivity or capacity. Here, the internal charge transfer process is quantified using a polythiophene loaded with 0, 25, or 100% nitroxide radicals (2,2,6,6-tetramethyl-1-piperidinyloxy [TEMPO]). Importantly, deconvolution of the cyclic voltammograms shows mixed faradaic and non-faradaic contributions that contribute to the internal charge transfer process. Further, mixed ion-electron transfer is determined for the 100% TEMPO-loaded conjugated radical polymer, from which it is estimated that one triflate anion and one propylene carbone molecule are exchanged for every electron. Although these findings indicate the reason behind their poor conductivity and capacity, they point to how these materials might be used as voltage regulators in the future.

Authors:
 [1];  [2];  [1];  [1];  [1];  [3];  [3]; ORCiD logo [4]
  1. Artie McFerrin Department of Chemical Engineering;Texas A&M University;College Station;USA
  2. Department of Materials Science and Engineering;Texas A&M University;College Station;USA
  3. Materials Science and Engineering;Cornell University;Ithaca;USA
  4. Artie McFerrin Department of Chemical Engineering;Texas A&M University;College Station;USA;Department of Materials Science and Engineering
Publication Date:
Research Org.:
Texas A & M Univ., College Station, TX (United States); Cornell Univ., Ithaca, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1658637
Alternate Identifier(s):
OSTI ID: 1706079
Grant/Contract Number:  
SC0014006; SC0014336
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 36; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Shaoyang, Easley, Alexandra D., Thakur, Ratul M., Ma, Ting, Yun, Junyeong, Zhang, Yiren, Ober, Christopher K., and Lutkenhaus, Jodie L. Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/d0sc03567j.
Wang, Shaoyang, Easley, Alexandra D., Thakur, Ratul M., Ma, Ting, Yun, Junyeong, Zhang, Yiren, Ober, Christopher K., & Lutkenhaus, Jodie L. Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers. United Kingdom. https://doi.org/10.1039/d0sc03567j
Wang, Shaoyang, Easley, Alexandra D., Thakur, Ratul M., Ma, Ting, Yun, Junyeong, Zhang, Yiren, Ober, Christopher K., and Lutkenhaus, Jodie L. Wed . "Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers". United Kingdom. https://doi.org/10.1039/d0sc03567j.
@article{osti_1658637,
title = {Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers},
author = {Wang, Shaoyang and Easley, Alexandra D. and Thakur, Ratul M. and Ma, Ting and Yun, Junyeong and Zhang, Yiren and Ober, Christopher K. and Lutkenhaus, Jodie L.},
abstractNote = {Macromolecular radicals are receiving growing interest as functional materials in energy storage devices and in electronics. With the need for enhanced conductivity, researchers have turned to macromolecular radicals bearing conjugated backbones, but results thus far have yielded conjugated radical polymers that are inferior in comparison to their non-conjugated partners. The emerging explanation is that the radical unit and the conjugated backbone (both being redox active) transfer electrons between each other, essentially “quenching” conductivity or capacity. Here, the internal charge transfer process is quantified using a polythiophene loaded with 0, 25, or 100% nitroxide radicals (2,2,6,6-tetramethyl-1-piperidinyloxy [TEMPO]). Importantly, deconvolution of the cyclic voltammograms shows mixed faradaic and non-faradaic contributions that contribute to the internal charge transfer process. Further, mixed ion-electron transfer is determined for the 100% TEMPO-loaded conjugated radical polymer, from which it is estimated that one triflate anion and one propylene carbone molecule are exchanged for every electron. Although these findings indicate the reason behind their poor conductivity and capacity, they point to how these materials might be used as voltage regulators in the future.},
doi = {10.1039/d0sc03567j},
journal = {Chemical Science},
number = 36,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {1}
}

Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/d0sc03567j

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Works referenced in this record:

Rechargeable batteries with organic radical cathodes
journal, June 2002


Conjugated Nitroxide Radical Polymers: Synthesis and Application in Flexible Energy Storage Devices
journal, January 2019

  • Xie, Yuan; Zhang, Kai; Monteiro, Michael J.
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 7
  • DOI: 10.1021/acsami.8b21073

V 2 O 5 -Anchored Carbon Nanotubes for Enhanced Electrochemical Energy Storage
journal, October 2011

  • Sathiya, M.; Prakash, A. S.; Ramesha, K.
  • Journal of the American Chemical Society, Vol. 133, Issue 40
  • DOI: 10.1021/ja207285b

Organic mixed ionic–electronic conductors
journal, August 2019


Impact of the synthesis method on the solid-state charge transport of radical polymers
journal, January 2018

  • Zhang, Yiren; Park, Albert; Cintora, Alicia
  • Journal of Materials Chemistry C, Vol. 6, Issue 1
  • DOI: 10.1039/C7TC04645F

Solution‐Processable Thermally Crosslinked Organic Radical Polymer Battery Cathodes
journal, March 2020

  • Wang, Shaoyang; Park, Albert Min Gyu; Flouda, Paraskevi
  • ChemSusChem, Vol. 13, Issue 9
  • DOI: 10.1002/cssc.201903554

Impact of the Addition of Redox-Active Salts on the Charge Transport Ability of Radical Polymer Thin Films
journal, June 2016


Charge transport in high-mobility conjugated polymers and molecular semiconductors
journal, April 2020


Charge Storage in Decyl- and 3,6,9-Trioxadecyl-Substituted Poly(dithieno[3,2- b :2,3- d ]pyrrole) Electrodes
journal, December 2013

  • Mike, Jared F.; Shao, Lin; Jeon, Ju-Won
  • Macromolecules, Vol. 47, Issue 1
  • DOI: 10.1021/ma402071k

Electrolyte anion-assisted charge transportation in poly(oxoammonium cation/nitroxyl radical) redox gels
journal, January 2012

  • Nakahara, Kentaro; Oyaizu, Kenichi; Nishide, Hiroyuki
  • Journal of Materials Chemistry, Vol. 22, Issue 27
  • DOI: 10.1039/c2jm31907a

Electrochemical Energy Storage in Poly(dithieno[3,2-b:2′,3′-d]pyrrole) Bearing Pendant Nitroxide Radicals
journal, July 2018


Electrochemical studies of some conducting polythiophene films
journal, April 1983

  • Waltman, Robert J.; Bargon, Joachim; Diaz, A. F.
  • The Journal of Physical Chemistry, Vol. 87, Issue 8
  • DOI: 10.1021/j100231a035

Oxidatively stable polyaniline:polyacid electrodes for electrochemical energy storage
journal, January 2013

  • Jeon, Ju-Won; Ma, Yuguang; Mike, Jared F.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 24
  • DOI: 10.1039/c3cp51620b

Unusual Internal Electron Transfer in Conjugated Radical Polymers
journal, August 2017

  • Li, Fei; Gore, Danielle N.; Wang, Shaoyang
  • Angewandte Chemie International Edition, Vol. 56, Issue 33
  • DOI: 10.1002/anie.201705204

Flexibility and High-Rate Discharge Properties of Organic Radical Batteries with Gel-State Electrodes
journal, January 2017

  • Iwasa, Shigeyuki; Nishi, Takanori; Sato, Hideyuki
  • Journal of The Electrochemical Society, Vol. 164, Issue 4
  • DOI: 10.1149/2.1631704jes

Diffusion-Cooperative Model for Charge Transport by Redox-Active Nonconjugated Polymers
journal, January 2018

  • Sato, Kan; Ichinoi, Rieka; Mizukami, Ryusuke
  • Journal of the American Chemical Society, Vol. 140, Issue 3
  • DOI: 10.1021/jacs.7b11272

Three-Step Redox in Polythiophenes:  Evidence from Electrochemistry at an Ultramicroelectrode
journal, January 1996

  • Chen, Xiwen; Inganäs, Olle
  • The Journal of Physical Chemistry, Vol. 100, Issue 37
  • DOI: 10.1021/jp9601779

A New Conducting Copolymer Bearing Electro‐Active Nitroxide Groups as Organic Electrode Materials for Batteries
journal, May 2020


The electrochemical performance of polythiophene synthesized by chemical method as the polymer battery electrode
journal, April 2004


Electrodeposition and properties of TEMPO functionalized polythiophene thin films
journal, January 2011


Synthesis of Poly(4-methacryloyloxy-TEMPO) via Group-Transfer Polymerization and Its Evaluation in Organic Radical Battery
journal, May 2007

  • Bugnon, Lucienne; Morton, Colin J. H.; Novak, Petr
  • Chemistry of Materials, Vol. 19, Issue 11
  • DOI: 10.1021/cm063052h

Synthesis and Properties of Polyacetylene and Polynorbornene Derivatives Carrying 2,2,5,5-Tetramethyl-1-pyrrolidinyloxy Moieties
journal, May 2007

  • Qu, Jinqing; Katsumata, Toru; Satoh, Masaharu
  • Macromolecules, Vol. 40, Issue 9
  • DOI: 10.1021/ma062357e

Charge Transport in Conjugated Polymers with Pendent Stable Radical Groups
journal, June 2018


Organic Radical Battery Approaching Practical Use
journal, March 2011

  • Nakahara, Kentaro; Oyaizu, Kenichi; Nishide, Hiroyuki
  • Chemistry Letters, Vol. 40, Issue 3
  • DOI: 10.1246/cl.2011.222

Polyacetylene and Polynorbornene Derivatives Carrying TEMPO. Synthesis and Properties as Organic Radical Battery Materials
journal, August 2006

  • Katsumata, Toru; Satoh, Masaharu; Wada, Jun
  • Macromolecular Rapid Communications, Vol. 27, Issue 15
  • DOI: 10.1002/marc.200600286

Electrochemical studies on doping of polyacetylene
journal, August 1984


Real-time insight into the doping mechanism of redox-active organic radical polymers
journal, November 2018


Electropolymerized Polythiophenes Bearing Pendant Nitroxide Radicals
journal, February 2016


Nernstian Adsorbate-like Bulk Layer of Organic Radical Polymers for High-Density Charge Storage Purposes
journal, November 2008

  • Oyaizu, Kenichi; Ando, Yuko; Konishi, Hiroaki
  • Journal of the American Chemical Society, Vol. 130, Issue 44
  • DOI: 10.1021/ja803742b

Encapsulation of organic active materials in carbon nanotubes for application to high-electrochemical-performance sodium batteries
journal, January 2016

  • Kim, Jae-Kwang; Kim, Yongil; Park, Seungyoung
  • Energy & Environmental Science, Vol. 9, Issue 4
  • DOI: 10.1039/C5EE02806J

Radical Polymers for Organic Electronic Devices: A Radical Departure from Conjugated Polymers?
journal, June 2009


Electrosynthesis and characterization of stable radical-functionalized oligo/polythiophenes
journal, January 2015

  • Almubayedh, Somaiah; Chahma, M'hamed
  • New Journal of Chemistry, Vol. 39, Issue 10
  • DOI: 10.1039/C5NJ01759A

Organic radical battery: nitroxide polymers as a cathode-active material
journal, November 2004


Controlled Radical Polymerization and Quantification of Solid State Electrical Conductivities of Macromolecules Bearing Pendant Stable Radical Groups
journal, October 2013

  • Rostro, Lizbeth; Baradwaj, Aditya G.; Boudouris, Bryan W.
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 20
  • DOI: 10.1021/am403223s

Polymer-Based Organic Batteries
journal, August 2016


PEDOT Radical Polymer with Synergetic Redox and Electrical Properties
journal, December 2015