Influence of Side-Chain Chemistry on Structure and Ionic Conduction Characteristics of Polythiophene Derivatives: A Computational and Experimental Study
Abstract
Although extensive efforts have been devoted to understanding electronic transport in conjugated polymers, little is known about their ionic conduction characteristics in relation to polymer chemistry, processing, and morphology. This work presents a combined computational and experimental study on morphology and ion transport in thin-film blends of polythiophene derivatives bearing oligoethylene glycol side-chains and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Using molecular dynamics (MD) simulation, we show that in the amorphous phase, the polythiophene derivative P3MEET bearing oligoethylene glycol side-chains with oxygen directly attached to the thiophene rings possesses lower Li+ ionic conductivity compared to its analog P3MEEMT that has a methyl spacer between the oxygen and the thiophene rings. Structural characterization of P3MEET and P3MEEMT thin film upon blending with LiTFSI indicates that adding LiTFSI expands the side-chain domains of the polymer crystallites and reduces the total degree of crystallinity at the same time. Moreover, LiTFSI is found to infiltrate both the amorphous and crystalline regimes at low concentrations but preferably resides in the amorphous domain at high LiTFSI concentrations. Ionic transport measured by electrochemical impedance spectroscopy in both P3MEET- and P3MEEMT-LiTFSI thin films is found to occur predominately in the amorphous domain, and ionic conductivity in P3MEEMT-LiTFSI is always higher thanmore »
- Authors:
-
[1];
[2];
[3];
[5];
[5]
- Univ. of Chicago, Chicago, IL (United States)
- Cornell Univ., Ithaca, NY (United States)
- Univ. of Washington, Seattle, WA (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- National Science Foundation (NSF); USDOE Office of Science (SC)
- OSTI Identifier:
- 1498068
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 4; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Conjugated polymer; LiTFSI; MD simulation; ionic conduction; mixed conduction; polar side-chains
Citation Formats
Dong, Ban Xuan, Nowak, Christian, Onorato, Jonathan W., Strzalka, Joseph, Escobedo, Fernando A., Luscombe, Christine K., Nealey, Paul F., and Patel, Shrayesh N. Influence of Side-Chain Chemistry on Structure and Ionic Conduction Characteristics of Polythiophene Derivatives: A Computational and Experimental Study. United States: N. p., 2019.
Web. doi:10.1021/acs.chemmater.8b05257.
Dong, Ban Xuan, Nowak, Christian, Onorato, Jonathan W., Strzalka, Joseph, Escobedo, Fernando A., Luscombe, Christine K., Nealey, Paul F., & Patel, Shrayesh N. Influence of Side-Chain Chemistry on Structure and Ionic Conduction Characteristics of Polythiophene Derivatives: A Computational and Experimental Study. United States. https://doi.org/10.1021/acs.chemmater.8b05257
Dong, Ban Xuan, Nowak, Christian, Onorato, Jonathan W., Strzalka, Joseph, Escobedo, Fernando A., Luscombe, Christine K., Nealey, Paul F., and Patel, Shrayesh N. Fri .
"Influence of Side-Chain Chemistry on Structure and Ionic Conduction Characteristics of Polythiophene Derivatives: A Computational and Experimental Study". United States. https://doi.org/10.1021/acs.chemmater.8b05257. https://www.osti.gov/servlets/purl/1498068.
@article{osti_1498068,
title = {Influence of Side-Chain Chemistry on Structure and Ionic Conduction Characteristics of Polythiophene Derivatives: A Computational and Experimental Study},
author = {Dong, Ban Xuan and Nowak, Christian and Onorato, Jonathan W. and Strzalka, Joseph and Escobedo, Fernando A. and Luscombe, Christine K. and Nealey, Paul F. and Patel, Shrayesh N.},
abstractNote = {Although extensive efforts have been devoted to understanding electronic transport in conjugated polymers, little is known about their ionic conduction characteristics in relation to polymer chemistry, processing, and morphology. This work presents a combined computational and experimental study on morphology and ion transport in thin-film blends of polythiophene derivatives bearing oligoethylene glycol side-chains and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Using molecular dynamics (MD) simulation, we show that in the amorphous phase, the polythiophene derivative P3MEET bearing oligoethylene glycol side-chains with oxygen directly attached to the thiophene rings possesses lower Li+ ionic conductivity compared to its analog P3MEEMT that has a methyl spacer between the oxygen and the thiophene rings. Structural characterization of P3MEET and P3MEEMT thin film upon blending with LiTFSI indicates that adding LiTFSI expands the side-chain domains of the polymer crystallites and reduces the total degree of crystallinity at the same time. Moreover, LiTFSI is found to infiltrate both the amorphous and crystalline regimes at low concentrations but preferably resides in the amorphous domain at high LiTFSI concentrations. Ionic transport measured by electrochemical impedance spectroscopy in both P3MEET- and P3MEEMT-LiTFSI thin films is found to occur predominately in the amorphous domain, and ionic conductivity in P3MEEMT-LiTFSI is always higher than in P3MEET-LiTFSI samples, consistent with predictions from MD simulations. As a result, our work provides a platform to predict and study the influence of polymer chemistry on the ionic conductivity of conjugated polymers.},
doi = {10.1021/acs.chemmater.8b05257},
journal = {Chemistry of Materials},
number = 4,
volume = 31,
place = {United States},
year = {Fri Feb 15 00:00:00 EST 2019},
month = {Fri Feb 15 00:00:00 EST 2019}
}
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