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Title: Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers

Abstract

Poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (PEO–POSS) mixed with lithium bis(trifluoromethanesulfonyl)imide salt is a nanostructured hybrid organic–inorganic block copolymer electrolyte that may enable lithium metal batteries. The synthesis and characteristics of three PEO–POSS block copolymer electrolytes which only differ by their POSS silica cage substituents (ethyl, isobutyl, and isooctyl) is reported. Changing the POSS monomer structure results in differences in both thermodynamics and ion transport. All three neat polymers exhibit lamellar morphologies. Adding salt results in the formation of a disordered window which closes and gives way to lamellae at higher salt concentrations. The width of disordered window decreases with increasing length of the POSS alkyl chain substituent from ethyl to isobutyl and is absent in the isooctyl sample. Rheological measurements demonstrate good mechanical rigidity when compared with similar all-organic block copolymers. While salt diffusion coefficient and current ratio are unaffected by substituent length, ionic conductivity increases as the length of the alkyl chain substituent decreases: the ethyl substituent is optimal for ion transport. Finally, this is surprising because conventional wisdom suggests that ion transport occurs primarily in the PEO-rich domains, that is, ion transport should be unaffected by substituent length after accounting for the minor change in conducting phase volume fraction.

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [3];  [4];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1601219
Alternate Identifier(s):
OSTI ID: 1581659
Grant/Contract Number:  
AC02-05CH11231; AC02-76SF00515; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Polymer Science
Additional Journal Information:
Journal Volume: 58; Journal Issue: 2; Journal ID: ISSN 2642-4150
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Gao, Kevin W., Jiang, Xi, Hoffman, Zach J., Sethi, Gurmukh K., Chakraborty, Saheli, Villaluenga, Irune, and Balsara, Nitash P. Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers. United States: N. p., 2020. Web. doi:10.1002/pol.20190073.
Gao, Kevin W., Jiang, Xi, Hoffman, Zach J., Sethi, Gurmukh K., Chakraborty, Saheli, Villaluenga, Irune, & Balsara, Nitash P. Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers. United States. https://doi.org/10.1002/pol.20190073
Gao, Kevin W., Jiang, Xi, Hoffman, Zach J., Sethi, Gurmukh K., Chakraborty, Saheli, Villaluenga, Irune, and Balsara, Nitash P. Wed . "Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers". United States. https://doi.org/10.1002/pol.20190073. https://www.osti.gov/servlets/purl/1601219.
@article{osti_1601219,
title = {Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers},
author = {Gao, Kevin W. and Jiang, Xi and Hoffman, Zach J. and Sethi, Gurmukh K. and Chakraborty, Saheli and Villaluenga, Irune and Balsara, Nitash P.},
abstractNote = {Poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (PEO–POSS) mixed with lithium bis(trifluoromethanesulfonyl)imide salt is a nanostructured hybrid organic–inorganic block copolymer electrolyte that may enable lithium metal batteries. The synthesis and characteristics of three PEO–POSS block copolymer electrolytes which only differ by their POSS silica cage substituents (ethyl, isobutyl, and isooctyl) is reported. Changing the POSS monomer structure results in differences in both thermodynamics and ion transport. All three neat polymers exhibit lamellar morphologies. Adding salt results in the formation of a disordered window which closes and gives way to lamellae at higher salt concentrations. The width of disordered window decreases with increasing length of the POSS alkyl chain substituent from ethyl to isobutyl and is absent in the isooctyl sample. Rheological measurements demonstrate good mechanical rigidity when compared with similar all-organic block copolymers. While salt diffusion coefficient and current ratio are unaffected by substituent length, ionic conductivity increases as the length of the alkyl chain substituent decreases: the ethyl substituent is optimal for ion transport. Finally, this is surprising because conventional wisdom suggests that ion transport occurs primarily in the PEO-rich domains, that is, ion transport should be unaffected by substituent length after accounting for the minor change in conducting phase volume fraction.},
doi = {10.1002/pol.20190073},
url = {https://www.osti.gov/biblio/1601219}, journal = {Journal of Polymer Science},
issn = {2642-4150},
number = 2,
volume = 58,
place = {United States},
year = {2020},
month = {1}
}

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