Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering

doi:https://doi.org/10.1021/acs.macromol.8b02142

Title: Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering

Abstract

In this work, crystallization in an ordered lamellar diblock copolymer/salt mixture, polystyrene-block-poly(ethylene oxide) mixed with lithium bis(trifluoromethanesulfonyl)imide salt (SEO/LiTFSI), has been studied using a combination of small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and depolarized light scattering (DPLS). Such materials have applications as electrolyte membranes in solid-state lithium batteries. The grain structure of the electrolyte was controlled by manipulating thermal history. Poly(ethylene oxide) (PEO) crystallization was confined within the microphase-separated morphology and did not affect the grain structure in the case of shallow quenches. Deep quenches resulted in unconfined crystallization, where crystal formation does not affect the microphase-separated morphology but does alter the grain structure. The difference between the two modes of crystallization can only be detected by DPLS. This knowledge is particularly relevant for nanostructured electrolytes wherein ion transport is a strong function of grain structure.

Authors:

Li, Xiuhong ^[1];

^[2];

^[3]; Wang, Xin ^[1]; Galluzzo, Michael D. ^[4];

^[2]; Wang, Andrew A. ^[2];

^[4];

^[1]

New York Univ. (NYU), NY (United States)
Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: 2019-01-23

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

OSTI Identifier:: 1594908

Grant/Contract Number:: AC02-05CH11231; DMR-1505476; DMR-1505444; AC02-76SF00515; DGE-1106400

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 52; Journal Issue: 3; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Scattering; Grain; Crystallization; Crystal structure; X-ray scattering

Citation Formats


                    Li, Xiuhong, Loo, Whitney S., Jiang, Xi, Wang, Xin, Galluzzo, Michael D., Mongcopa, Katrina I., Wang, Andrew A., Balsara, Nitash P., and Garetz, Bruce A. Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering.  United States: N. p., 2019. 
        Web.  doi:10.1021/acs.macromol.8b02142.

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                    Li, Xiuhong, Loo, Whitney S., Jiang, Xi, Wang, Xin, Galluzzo, Michael D., Mongcopa, Katrina I., Wang, Andrew A., Balsara, Nitash P., & Garetz, Bruce A. Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering.  United States.  https://doi.org/10.1021/acs.macromol.8b02142

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                    Li, Xiuhong, Loo, Whitney S., Jiang, Xi, Wang, Xin, Galluzzo, Michael D., Mongcopa, Katrina I., Wang, Andrew A., Balsara, Nitash P., and Garetz, Bruce A. Wed .  
        "Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering".  United States.  https://doi.org/10.1021/acs.macromol.8b02142.  https://www.osti.gov/servlets/purl/1594908.

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@article{osti_1594908,

  title        = {Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering},

  author       = {Li, Xiuhong and Loo, Whitney S. and Jiang, Xi and Wang, Xin and Galluzzo, Michael D. and Mongcopa, Katrina I. and Wang, Andrew A. and Balsara, Nitash P. and Garetz, Bruce A.},

  abstractNote = {In this work, crystallization in an ordered lamellar diblock copolymer/salt mixture, polystyrene-block-poly(ethylene oxide) mixed with lithium bis(trifluoromethanesulfonyl)imide salt (SEO/LiTFSI), has been studied using a combination of small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and depolarized light scattering (DPLS). Such materials have applications as electrolyte membranes in solid-state lithium batteries. The grain structure of the electrolyte was controlled by manipulating thermal history. Poly(ethylene oxide) (PEO) crystallization was confined within the microphase-separated morphology and did not affect the grain structure in the case of shallow quenches. Deep quenches resulted in unconfined crystallization, where crystal formation does not affect the microphase-separated morphology but does alter the grain structure. The difference between the two modes of crystallization can only be detected by DPLS. This knowledge is particularly relevant for nanostructured electrolytes wherein ion transport is a strong function of grain structure.},

  doi          = {10.1021/acs.macromol.8b02142},

  url          = {https://www.osti.gov/biblio/1594908},
  journal      = {Macromolecules},

  issn         = {0024-9297},

  number       = 3,

  volume       = 52,

  place        = {United States},

  year         = {2019},

  month        = {1}

}

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https://doi.org/10.1021/acs.macromol.8b02142

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Works referencing / citing this record:

Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes
journal, July 2019

Galluzzo, Michael D.; Maslyn, Jacqueline A.; Shah, Deep B.
The Journal of Chemical Physics, Vol. 151, Issue 2
https://doi.org/10.1063/1.5109684

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Title: Confined versus Unconfined Crystallization in Block Copolymer/Salt Mixtures Studied by Depolarized Light Scattering

Abstract

Citation Formats

Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes journal, July 2019

Ohm’s law for ion conduction in lithium and beyond-lithium battery electrolytes
journal, July 2019