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Title: The impact of radical loading and oxidation on the conformation of organic radical polymers by small angle neutron scattering

Abstract

Electrodes comprised of organic polymeric materials containing stable radicals have become attractive for incorporation into organic radical batteries. Specifically, the radical polymer poly(2,2,6,6-tetramethylpeperidinyloxy-4-yl methacrylate) (PTMA) exhibits extremely rapid electron charge transport rates, comparable to traditional transition metal ions. However, the structural reorganization that the polymer undergoes during charging is not well understood. Using small angle neutron scattering, we have investigated the structural changes the PTMA polymer exhibits with variation of radical concentration or oxidation. The results indicate that as the radical concentration is increased, the polymer becomes more inflexible and begins to aggregate with neighboring polymer chains as the radicals on the polymer align with neighboring solvated chains. Additional studies monitor the conformational changes of the PTMA copolymers with oxidation to mimic the structural changes that the polymer undergoes during charging. These results show that polymers with low radical densities are more susceptible to reorientation with charging than a polymer that is fully saturated with radical moieties. This study therefore provides seminal fundamental information that identifies the relationship between radical density and molecular structure providing crucial insight that is needed to improve the performance of organic radical batteries.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2];  [3]; ORCiD logo [4]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
  4. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1468737
Alternate Identifier(s):
OSTI ID: 1462136; OSTI ID: 1511945
Report Number(s):
NREL/JA-5900-71704
Journal ID: ISSN 2050-7488; JMCAET
Grant/Contract Number:  
AC36-08GO28308; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 32; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; metal ions; organic polymers; oxidation; secondary batteries; transition metal compounds; transition metals

Citation Formats

Martin, Halie J., Hughes, Barbara K., Braunecker, Wade A., Gennett, Thomas, and Dadmun, Mark D. The impact of radical loading and oxidation on the conformation of organic radical polymers by small angle neutron scattering. United States: N. p., 2018. Web. doi:10.1039/C8TA04583F.
Martin, Halie J., Hughes, Barbara K., Braunecker, Wade A., Gennett, Thomas, & Dadmun, Mark D. The impact of radical loading and oxidation on the conformation of organic radical polymers by small angle neutron scattering. United States. doi:10.1039/C8TA04583F.
Martin, Halie J., Hughes, Barbara K., Braunecker, Wade A., Gennett, Thomas, and Dadmun, Mark D. Mon . "The impact of radical loading and oxidation on the conformation of organic radical polymers by small angle neutron scattering". United States. doi:10.1039/C8TA04583F. https://www.osti.gov/servlets/purl/1468737.
@article{osti_1468737,
title = {The impact of radical loading and oxidation on the conformation of organic radical polymers by small angle neutron scattering},
author = {Martin, Halie J. and Hughes, Barbara K. and Braunecker, Wade A. and Gennett, Thomas and Dadmun, Mark D.},
abstractNote = {Electrodes comprised of organic polymeric materials containing stable radicals have become attractive for incorporation into organic radical batteries. Specifically, the radical polymer poly(2,2,6,6-tetramethylpeperidinyloxy-4-yl methacrylate) (PTMA) exhibits extremely rapid electron charge transport rates, comparable to traditional transition metal ions. However, the structural reorganization that the polymer undergoes during charging is not well understood. Using small angle neutron scattering, we have investigated the structural changes the PTMA polymer exhibits with variation of radical concentration or oxidation. The results indicate that as the radical concentration is increased, the polymer becomes more inflexible and begins to aggregate with neighboring polymer chains as the radicals on the polymer align with neighboring solvated chains. Additional studies monitor the conformational changes of the PTMA copolymers with oxidation to mimic the structural changes that the polymer undergoes during charging. These results show that polymers with low radical densities are more susceptible to reorientation with charging than a polymer that is fully saturated with radical moieties. This study therefore provides seminal fundamental information that identifies the relationship between radical density and molecular structure providing crucial insight that is needed to improve the performance of organic radical batteries.},
doi = {10.1039/C8TA04583F},
journal = {Journal of Materials Chemistry. A},
number = 32,
volume = 6,
place = {United States},
year = {2018},
month = {7}
}

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