Role of Defects in Ion Transport in Block Copolymer Electrolytes

Kambe, Yu; Arges, Christopher G.; Czaplewski, David A.; Dolejsi, Moshe; Krishnan, Satya; Stoykovich, Mark P.; de Pablo, Juan J.; Nealey, Paul F.

doi:10.1021/acs.nanolett.9b01758

Title: Role of Defects in Ion Transport in Block Copolymer Electrolytes

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Abstract

Ion conducting block copolymers can overcome traditional limitations of homopolymer electrolytes by phase separating into nanoarchitectures that can be simultaneously optimized for two or more orthogonal material properties such as high ionic conductivity and mechanical stability. A key challenge in understanding the ion transport properties of these materials is the difficulty of extracting structure-function relationships without having complete knowledge of all nanoscale transport pathways in bulk samples. In this paper, we demonstrate a method for deriving structure-transport relationships for ion conducting block copolymers using thin films and interdigitated electrodes. Well-defined and directly imaged structure in films of poly(styrene)-block-poly(2-vinylpyridine) is controlled using techniques of directed self-assembly then the poly(2-vinylpyridine) is selectively converted into an ion conductor. The ion conductivity is found to be directly proportional to the total number of connected paths between electrodes and the path length. A single defect such as a dislocation anywhere in the path of an ion conducting route disconnects and precludes that pathway from contributing to the conductivity and results in an increase in the dielectric parameter of the film. When all the ion conduction pathways are blocked between electrodes, the conductivity is negligible, 4 orders of magnitude lower compared to a completely connected morphologymore »« less

Authors:

^[1];

^[2]; Czaplewski, David A. ^[3]; Dolejsi, Moshe ^[1]; Krishnan, Satya ^[4]; Stoykovich, Mark P. ^[4];

^[1];

^[1]

Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Louisiana State Univ., Baton Rouge, LA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Univ. of Chicago, IL (United States)

Publication Date:: Mon Jun 24 00:00:00 EDT 2019

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

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

OSTI Identifier:: 1560016

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Nano Letters

Additional Journal Information:: Journal Volume: 19; Journal Issue: 7; Journal ID: ISSN 1530-6984

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; block copolymer electrolytes; directed assembly; ion transport; thin film

Citation Formats


                    Kambe, Yu, Arges, Christopher G., Czaplewski, David A., Dolejsi, Moshe, Krishnan, Satya, Stoykovich, Mark P., de Pablo, Juan J., and Nealey, Paul F. Role of Defects in Ion Transport in Block Copolymer Electrolytes.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.nanolett.9b01758.

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                    Kambe, Yu, Arges, Christopher G., Czaplewski, David A., Dolejsi, Moshe, Krishnan, Satya, Stoykovich, Mark P., de Pablo, Juan J., & Nealey, Paul F. Role of Defects in Ion Transport in Block Copolymer Electrolytes.  United States.  https://doi.org/10.1021/acs.nanolett.9b01758

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                    Kambe, Yu, Arges, Christopher G., Czaplewski, David A., Dolejsi, Moshe, Krishnan, Satya, Stoykovich, Mark P., de Pablo, Juan J., and Nealey, Paul F. Mon .  
"Role of Defects in Ion Transport in Block Copolymer Electrolytes".  United States.  https://doi.org/10.1021/acs.nanolett.9b01758.  https://www.osti.gov/servlets/purl/1560016.

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@article{osti_1560016,

  title        = {Role of Defects in Ion Transport in Block Copolymer Electrolytes},

  author       = {Kambe, Yu and Arges, Christopher G. and Czaplewski, David A. and Dolejsi, Moshe and Krishnan, Satya and Stoykovich, Mark P. and de Pablo, Juan J. and Nealey, Paul F.},

  abstractNote = {Ion conducting block copolymers can overcome traditional limitations of homopolymer electrolytes by phase separating into nanoarchitectures that can be simultaneously optimized for two or more orthogonal material properties such as high ionic conductivity and mechanical stability. A key challenge in understanding the ion transport properties of these materials is the difficulty of extracting structure-function relationships without having complete knowledge of all nanoscale transport pathways in bulk samples. In this paper, we demonstrate a method for deriving structure-transport relationships for ion conducting block copolymers using thin films and interdigitated electrodes. Well-defined and directly imaged structure in films of poly(styrene)-block-poly(2-vinylpyridine) is controlled using techniques of directed self-assembly then the poly(2-vinylpyridine) is selectively converted into an ion conductor. The ion conductivity is found to be directly proportional to the total number of connected paths between electrodes and the path length. A single defect such as a dislocation anywhere in the path of an ion conducting route disconnects and precludes that pathway from contributing to the conductivity and results in an increase in the dielectric parameter of the film. When all the ion conduction pathways are blocked between electrodes, the conductivity is negligible, 4 orders of magnitude lower compared to a completely connected morphology and the dielectric parameter increases by a factor of 50. Lastly, these results have profound implications for the interpretation, design, and processing of block copolymer electrolytes for applications as ion conducting membranes.},

  doi          = {10.1021/acs.nanolett.9b01758},

  journal      = {Nano Letters},

  number       = 7,

  volume       = 19,

  place        = {United States},

  year         = {Mon Jun 24 00:00:00 EDT 2019},

  month        = {Mon Jun 24 00:00:00 EDT 2019}

}

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