Ion Transport in 2D Nanostructured $\pi$-Conjugated Thieno[3,2-b]thiophene-Based Liquid Crystal

Wang, Zhongyang; Wang, Chaoqiuyu; Sun, Yangyang; Wang, Kai; Strzalka, Joseph W.; Patel, Shrayesh N.; Nealey, Paul F.; Ober, Christopher K.; Escobedo, Fernando A.

doi:10.1021/acsnano.2c07789

Ion Transport in 2D Nanostructured $$\pi$$-Conjugated Thieno[3,2-b]thiophene-Based Liquid Crystal

Journal Article · Wed Dec 07 00:00:00 EST 2022 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.2c07789· OSTI ID:1909462

^[1]; Wang, Chaoqiuyu ^[2]; ^[2]; Wang, Kai ^[1]; ^[3]; ^[1]; ^[1]; ^[2]; ^[2]

Univ. of Chicago, IL (United States)
Cornell Univ., Ithaca, NY (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)

Leveraging the self-assembling behavior of liquid crystals designed for controlling ion transport is of both fundamental and technological significance. Here, we have designed and prepared a liquid crystal that contains (2,5-bis(5-(2,5,8,11-tetraoxatridecan-13-yl)thiophen-2yl)thieno[3,2-b]thiophene (BTTT) as mesogenic core and conjugated segment and symmetric tetra(ethylene oxide) (EO4) as polar side chains for ionic conducting regions. Driven by the crystallization of the BTTT cores, BTTT/dEO4 exhibits well-ordered smectic phases below 71.5 °C as confirmed by differential scanning calorimetry, polarized optical microscope, temperature dependent wide-angle X-ray scattering and grazing incidence wide-angle X-ray scattering (GIWAXS). We adopted a combination of experimental GIWAXS and molecular dynamics (MD) simulations to better understand the molecular packing of BTTT/dEO4 films, particularly when loaded with the ion conducting salt, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Ionic conduction of BTTT/dEO4 is realized by the addition of LiTFSI, with the material able to maintain smectic phases up to r = [Li⁺]/[EO] = 0.1. In this work, The highest ionic conductivity of 8 × 10^-3 S/cm was attained at an intermedium salt concentration of r = 0.05. It was also found that ion conduction in BTTT/dEO4 is enhanced by forming a smectic layered structure with irregular interfaces between the BTTT and EO4 layers and by the lateral film expansion upon salt addition. This can be explained by the enhancement of the misalignment and configurational entropy of the side chains, which increase their local mobility and that of the solvated ions. Our molecular design thus illustrates how, beyond the favorable energetic interactions that drive the assembly and ion solvating domains, modulation of entropic effects can also be favorably harnessed to improve ion conduction.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1909462

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 12 Vol. 16; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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