Charge Transport in Imidazolium-Based Homo- and Triblock Poly(ionic liquid)s

Mapesa, Emmanuel U.; Chen, Mingtao; Heres, Maximilian F.; Harris, Matthew A.; Kinsey, Thomas; Wang, Yangyang; Long, Timothy E.; Lokitz, Bradley S.; Sangoro, Joshua R.

doi:10.1021/acs.macromol.8b02143

Title: Charge Transport in Imidazolium-Based Homo- and Triblock Poly(ionic liquid)s

Full Record
Other Related Research

Abstract

Ion dynamics in a series of imidazolium-based triblock copolymers (triblock co-PILs) are investigated using broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC) and compared to their homopolymer counterparts (homo-PILs). Two calorimetric glass transition temperatures (T_g) are observed corresponding to the charged poly(ionic liquid) (PIL) blocks and noncharged polystyrene (PS) blocks. Varying the counterion from Br^– to NTf₂– decreases the T_g of the charged block by over 50 °C, thereby increasing the room-temperature ionic dc conductivity by over 6 orders of magnitude. Interestingly, for a given anion, varying the volume fraction of the charged block, from ~0.5 to ~0.8, has very minimal effect on the dc ionic conductivity, indicating that the choice of counterion is the key factor influencing charge transport in these systems.

Authors:

^[1]; Chen, Mingtao ^[2]; Heres, Maximilian F. ^[1]; Harris, Matthew A. ^[1];

^[1];

^[3];

^[2];

^[3];

^[1]

Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States). Dept. of Chemistry, Macromolecules Innovation Inst. (MII)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Publication Date:: Thu Jan 03 00:00:00 EST 2019

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1491305

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 52; Journal Issue: 2; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Mapesa, Emmanuel U., Chen, Mingtao, Heres, Maximilian F., Harris, Matthew A., Kinsey, Thomas, Wang, Yangyang, Long, Timothy E., Lokitz, Bradley S., and Sangoro, Joshua R. Charge Transport in Imidazolium-Based Homo- and Triblock Poly(ionic liquid)s.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.macromol.8b02143.

Copy to clipboard


                    Mapesa, Emmanuel U., Chen, Mingtao, Heres, Maximilian F., Harris, Matthew A., Kinsey, Thomas, Wang, Yangyang, Long, Timothy E., Lokitz, Bradley S., & Sangoro, Joshua R. Charge Transport in Imidazolium-Based Homo- and Triblock Poly(ionic liquid)s.  United States.  https://doi.org/10.1021/acs.macromol.8b02143

Copy to clipboard


                    Mapesa, Emmanuel U., Chen, Mingtao, Heres, Maximilian F., Harris, Matthew A., Kinsey, Thomas, Wang, Yangyang, Long, Timothy E., Lokitz, Bradley S., and Sangoro, Joshua R. Thu .  
"Charge Transport in Imidazolium-Based Homo- and Triblock Poly(ionic liquid)s".  United States.  https://doi.org/10.1021/acs.macromol.8b02143.  https://www.osti.gov/servlets/purl/1491305.

Copy to clipboard


                    
@article{osti_1491305,

  title        = {Charge Transport in Imidazolium-Based Homo- and Triblock Poly(ionic liquid)s},

  author       = {Mapesa, Emmanuel U. and Chen, Mingtao and Heres, Maximilian F. and Harris, Matthew A. and Kinsey, Thomas and Wang, Yangyang and Long, Timothy E. and Lokitz, Bradley S. and Sangoro, Joshua R.},

  abstractNote = {Ion dynamics in a series of imidazolium-based triblock copolymers (triblock co-PILs) are investigated using broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC) and compared to their homopolymer counterparts (homo-PILs). Two calorimetric glass transition temperatures (Tg) are observed corresponding to the charged poly(ionic liquid) (PIL) blocks and noncharged polystyrene (PS) blocks. Varying the counterion from Br– to NTf2– decreases the Tg of the charged block by over 50 °C, thereby increasing the room-temperature ionic dc conductivity by over 6 orders of magnitude. Interestingly, for a given anion, varying the volume fraction of the charged block, from ~0.5 to ~0.8, has very minimal effect on the dc ionic conductivity, indicating that the choice of counterion is the key factor influencing charge transport in these systems.},

  doi          = {10.1021/acs.macromol.8b02143},

  journal      = {Macromolecules},

  number       = 2,

  volume       = 52,

  place        = {United States},

  year         = {Thu Jan 03 00:00:00 EST 2019},

  month        = {Thu Jan 03 00:00:00 EST 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.macromol.8b02143

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 9 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Imidazolium-containing, hydrophobic-ionic-hydrophilic ABC triblock copolymers: synthesis, ordered phase-separation, and supported membrane fabrication

Journal Article Wiesenauer, EF ; Nguyen, PT ; Newell, BS ; ... - Soft Matter

Novel ABC triblock copolymers containing hydrophobic, imidazolium ionic liquid (IL)-based ionic, and non-charged hydrophilic blocks were synthesized by direct sequential, ring-opening metathesis polymerization (ROMP) of three chemically immiscible norborene monomers. The resulting ABC triblock copolymers were found by small-angle X-ray scattering to phase-separate into different nanostructures in their pure melt states, depending on their block sequence and compositions. Supported composite membranes of these triblock copolymers were successfully fabricated with defect-free, <= 20 microns thick top coatings. Preliminary CO2/light gas transport studies demonstrated the potential of this new type of IL-based block copolymer material for gas separation applications.
https://doi.org/10.1039/c3sm51085a
Design and Gas Separation Performance of Imidazolium Poly(ILs) Containing Multivalent Imidazolium Fillers and Crosslinking Agents

Journal Article O’Harra, Kathryn E. ; DeVriese, Emily M. ; Turflinger, Erika M. ; ... - Polymers

This work introduces a series of vinyl-imidazolium-based polyelectrolyte composites, which were structurally modified via impregnation with multivalent imidazolium-benzene ionic liquids (ILs) or crosslinked with novel cationic crosslinkers which possess internal imidazolium cations and vinylimidazolium cations at the periphery. A set of eight [C₄vim][Tf₂N]-based membranes were prepared via UV-initiated free radical polymerization, including four composites containing di-, tri-, tetra-, and hexa-imidazolium benzene ILs and four crosslinked derivatives which utilized tri- and tetra- vinylimidazolium benzene crosslinking agents. Structural and functional characterizations were performed, and pure gas permeation data were collected to better understand the effects of “free” ILs dispersed in the polymericmore »« less
https://doi.org/10.3390/polym13091388
Synthesis of Poly(ionic Liquid)s-block-poly(methyl Methacrylate) Copolymer-Grafted Silica Particle Brushes with Enhanced CO₂ Permeability and Mechanical Performance

Journal Article Wang, Zongyu ; Wang, Yangyang ; Chen, Jihua ; ... - Langmuir

Poly(ionic liquid) (PIL)-based block copolymers are of particular interest as they combine the specific properties of PILs with the self-assembling behaviors of block copolymers, broadening the range of potential applications for PIL-based materials. In this work, three particle brushes: SiO₂-g-poly(methyl methacrylate) (PMMA), SiO₂-g-PIL, and SiO₂-g-PMMA-b-PIL were prepared through surface-initiated atom transfer radical polymerization. Unlike the homogeneous homopolymer particle brushes, the block copolymer particle brush SiO₂-g-PMMA-b-PIL exhibited a bimodal chain architecture and unique phase-separated morphology, which were confirmed by size-exclusion chromatography and transmission electron microscopy. In addition, the influence of the introduction of the PMMA segment on the gas separation andmore »« less
https://doi.org/10.1021/acs.langmuir.1c01877

Full Text Available
Enhanced Conductivity via Homopolymer-Rich Pathways in Block Polymer-Blended Electrolytes

Journal Article Morris, Melody A. ; Sung, Seung Hyun ; Ketkar, Priyanka M. ; ... - Macromolecules

The optimization of ionic conductivity and lithium-ion battery stability can be achieved by independently tuning the ion transport and mechanical robustness of block polymer (BP) electrolytes. However, the ionic conductivity of BP electrolytes is inherently limited by the covalent attachment of the ionically conductive block to the mechanically robust block, among other factors. Herein, the BP electrolyte polystyrene-block-poly(oligo-oxyethylene methacrylate) [PS-b-POEM] was blended with POEM homopolymers of varying molecular weights. The incorporation of a higher molecular weight homopolymer additive (α > 1 state) promoted a “dry brush-like” homopolymer distribution within the BP self-assembly and led to higher lithium salt concentrations inmore »« less
Cited by 21
https://doi.org/10.1021/acs.macromol.9b01879

Full Text Available
Influence of Short Central PEO Segment on Hydrolytic and Enzymatic Degradation of Triblock PCL Copolymers

Journal Article Ponjavic, Marijana ; Nikolic, Marija S. ; Jeremic, Sanja ; ... - Journal of Polymers and the Environment

Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (M{sub n} 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by {sup 1}H NMR, quantitative {sup 13}C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (< 2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss,more »« less
https://doi.org/10.1007/S10924-017-1130-2

Similar Records