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

Gao, Kevin W.; Jiang, Xi; Hoffman, Zach J.; Sethi, Gurmukh K.; Chakraborty, Saheli; Villaluenga, Irune; Balsara, Nitash P.

doi:10.1002/pol.20190073

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

Journal Article · Tue Jan 07 23:00:00 EST 2020 · Journal of Polymer Science

DOI:https://doi.org/10.1002/pol.20190073· OSTI ID:1601219

^[1]; Jiang, Xi ^[2]; Hoffman, Zach J. ^[1]; Sethi, Gurmukh K. ^[3]; Chakraborty, Saheli ^[3]; Villaluenga, Irune ^[4]; Balsara, Nitash P. ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Energy Storage Research (JCESR)
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)
Univ. of California, Berkeley, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; AC02-06CH11357

OSTI ID:: 1601219

Alternate ID(s):: OSTI ID: 1581659

Journal Information:: Journal of Polymer Science, Journal Name: Journal of Polymer Science Journal Issue: 2 Vol. 58; ISSN 2642-4150

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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