Ion Transport in Pendant and Backbone Polymerized Ionic Liquids

Preeya Kuray; Takeru Noda; Atsushi Matsumoto; Ciprian Iacob; Tadashi Inoue; Michael A. Hickner; James Runt

doi:10.1021/acs.macromol.8b02682

Ion Transport in Pendant and Backbone Polymerized Ionic Liquids

Preeya Kuray, Takeru Noda, Atsushi Matsumoto, Ciprian Iacob, Tadashi Inoue, Michael A. Hickner, James Runt

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

Polymerized ionic liquids (PILs) are single-ion conductors in which one of the ionic species is tethered to the polymer chain while the other is free to be transported. The ionic species can either be directly incorporated into the polymeric backbone (backbone PILs) or placed as pendant groups to the chain (pendant PILs). Here, we examined the morphology, conductivity, and rheology of imidazolium-based pendant and backbone PILs. We found that pendant PILs yielded higher ionic conductivity when scaled to T_g, but backbone PILs exhibited higher ionic conductivity on an absolute temperature scale, likely because of differences in the T_gs of the two systems. We also found that ion transport for backbone PILs was coupled to the segmental dynamics below T_g, where the decoupling of ionic conductivity from segmental relaxation was observed for pendant PILs. The results of this study will help the community to better understand the role of the PIL structure on conductivity to work toward the ultimate goal of designing high-performance solid polymer electrolytes.

Original language	English (US)
Journal	Macromolecules
DOIs	https://doi.org/10.1021/acs.macromol.8b02682
State	Accepted/In press - 2018

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acs.macromol.8b02682

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@article{ebd04397c7cd43a1ac93d9162e7c0b84,

title = "Ion Transport in Pendant and Backbone Polymerized Ionic Liquids",

abstract = "Polymerized ionic liquids (PILs) are single-ion conductors in which one of the ionic species is tethered to the polymer chain while the other is free to be transported. The ionic species can either be directly incorporated into the polymeric backbone (backbone PILs) or placed as pendant groups to the chain (pendant PILs). Here, we examined the morphology, conductivity, and rheology of imidazolium-based pendant and backbone PILs. We found that pendant PILs yielded higher ionic conductivity when scaled to Tg, but backbone PILs exhibited higher ionic conductivity on an absolute temperature scale, likely because of differences in the Tgs of the two systems. We also found that ion transport for backbone PILs was coupled to the segmental dynamics below Tg, where the decoupling of ionic conductivity from segmental relaxation was observed for pendant PILs. The results of this study will help the community to better understand the role of the PIL structure on conductivity to work toward the ultimate goal of designing high-performance solid polymer electrolytes.",

author = "Preeya Kuray and Takeru Noda and Atsushi Matsumoto and Ciprian Iacob and Tadashi Inoue and Hickner, {Michael A.} and James Runt",

note = "Funding Information: The authors thank Nichole Wonderling and Natalie Mamrol for assisting in X-ray scattering experiments in the Penn State Materials Research Institute Materials Characterization Lab and Renxuan Xie and Albree Weisen for assisting in sample preparation. This work was supported by the National Science Foundation and Japanese Society for the Promotion of Science East Asian Pacific Summer Institute Fellowship (award #: 1713929) and by (DMR-1505953 to JPR). The authors of this work also gratefully acknowledge the support of the Okinawa Institute of Science and Technology Graduate University with subsidy funding from the Cabinet Office, Government of Japan. Finally, we would like to acknowledge the financial support of the project PN 19110204 by the Romanian Ministry of Scientific Research and Innovation.",

year = "2018",

doi = "10.1021/acs.macromol.8b02682",

language = "English (US)",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

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T1 - Ion Transport in Pendant and Backbone Polymerized Ionic Liquids

AU - Kuray, Preeya

AU - Noda, Takeru

AU - Matsumoto, Atsushi

AU - Iacob, Ciprian

AU - Inoue, Tadashi

AU - Hickner, Michael A.

AU - Runt, James

N1 - Funding Information: The authors thank Nichole Wonderling and Natalie Mamrol for assisting in X-ray scattering experiments in the Penn State Materials Research Institute Materials Characterization Lab and Renxuan Xie and Albree Weisen for assisting in sample preparation. This work was supported by the National Science Foundation and Japanese Society for the Promotion of Science East Asian Pacific Summer Institute Fellowship (award #: 1713929) and by (DMR-1505953 to JPR). The authors of this work also gratefully acknowledge the support of the Okinawa Institute of Science and Technology Graduate University with subsidy funding from the Cabinet Office, Government of Japan. Finally, we would like to acknowledge the financial support of the project PN 19110204 by the Romanian Ministry of Scientific Research and Innovation.

PY - 2018

Y1 - 2018

N2 - Polymerized ionic liquids (PILs) are single-ion conductors in which one of the ionic species is tethered to the polymer chain while the other is free to be transported. The ionic species can either be directly incorporated into the polymeric backbone (backbone PILs) or placed as pendant groups to the chain (pendant PILs). Here, we examined the morphology, conductivity, and rheology of imidazolium-based pendant and backbone PILs. We found that pendant PILs yielded higher ionic conductivity when scaled to Tg, but backbone PILs exhibited higher ionic conductivity on an absolute temperature scale, likely because of differences in the Tgs of the two systems. We also found that ion transport for backbone PILs was coupled to the segmental dynamics below Tg, where the decoupling of ionic conductivity from segmental relaxation was observed for pendant PILs. The results of this study will help the community to better understand the role of the PIL structure on conductivity to work toward the ultimate goal of designing high-performance solid polymer electrolytes.

AB - Polymerized ionic liquids (PILs) are single-ion conductors in which one of the ionic species is tethered to the polymer chain while the other is free to be transported. The ionic species can either be directly incorporated into the polymeric backbone (backbone PILs) or placed as pendant groups to the chain (pendant PILs). Here, we examined the morphology, conductivity, and rheology of imidazolium-based pendant and backbone PILs. We found that pendant PILs yielded higher ionic conductivity when scaled to Tg, but backbone PILs exhibited higher ionic conductivity on an absolute temperature scale, likely because of differences in the Tgs of the two systems. We also found that ion transport for backbone PILs was coupled to the segmental dynamics below Tg, where the decoupling of ionic conductivity from segmental relaxation was observed for pendant PILs. The results of this study will help the community to better understand the role of the PIL structure on conductivity to work toward the ultimate goal of designing high-performance solid polymer electrolytes.

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SN - 0024-9297

ER -

Ion Transport in Pendant and Backbone Polymerized Ionic Liquids

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