Reentrant phase behavior and coexistence in asymmetric block copolymer electrolytes

Loo, Whitney S.; Jiang, Xi; Maslyn, Jacqueline A.; Oh, Hee Jeung; Zhu, Chenhui; Downing, Kenneth H.; Balsara, Nitash P.

doi:10.1039/c8sm00175h

Reentrant phase behavior and coexistence in asymmetric block copolymer electrolytes

Journal Article · Wed Mar 07 00:00:00 EST 2018 · Soft Matter

DOI:https://doi.org/10.1039/c8sm00175h· OSTI ID:1476591

^[1]; Jiang, Xi ^[2]; Maslyn, Jacqueline A. ^[3]; Oh, Hee Jeung ^[1]; Zhu, Chenhui ^[4]; ^[5]; ^[6]

Univ. of California, Berkeley, CA (United States). Department of Chemical and Biomolecular Engineering
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Univ. of California, Berkeley, CA (United States). Department of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division
Univ. of California, Berkeley, CA (United States). Department of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division and Energy Technologies Division

It is known that the addition of salts to symmetric block copolymers leads to stabilization of ordered phases and an increase in domain spacing; both trends are consistent with an increase in the effective Flory-Huggins interaction parameter between the blocks, χ. In this work, we show that the addition of salt to a disordered asymmetric block copolymer first leads to the formation of coexisting ordered phases which give way to a reentrant disordered phase at a higher salt concentration. The coexisting phases are both body centered cubic (BCC) with different domain spacings, stabilized by partitioning of the salt. Further increase in salt concentration results in yet another disorder-to-order transition; hexagonally packed cylinders are obtained in the high salt concentration limit. The coexisting phases formed at intermediate salt concentration, elucidated by electron tomography, showed the absence of macroscopic regions with distinct BCC lattices. A different asymmetric block copolymer with composition in the vicinity of the sample described above only showed only a single disorder-to-order transition. However, the dependence of domain spacing on salt concentration was distinctly non-monotonic, and similar to that of the sample with the reentrant phase behavior. This dependence appears to be an announcement of reentrant phase transitions in asymmetric block copolymer electrolytes. These results cannot be mapped on to the traditional theory of block copolymer electrolyte self-assembly based on an effective χ.

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); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

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

OSTI ID:: 1476591

Alternate ID(s):: OSTI ID: 1434131

Journal Information:: Soft Matter, Journal Name: Soft Matter Journal Issue: 15 Vol. 14; ISSN SMOABF; ISSN 1744-683X

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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