Block copolymer synthesis in ionic liquid via polymerisation-induced self-assembly: A convenient route to gel electrolytes

Abstract

We report for the first time a reversible addition–fragmentation chain transfer polymerisation-induced self-assembly (RAFT-PISA) formulation in ionic liquid (IL) that yields worm gels. A series of poly(2-hydroxyethyl methacrylate)-b-poly(benzyl methacrylate) (PHEMA-b-PBzMA) block copolymer nanoparticles were synthesised via RAFT dispersion polymerisation of benzyl methacrylate in the hydrophilic IL 1-ethyl-3-methyl imidazolium dicyanamide, [EMIM][DCA]. This RAFT-PISA formulation can be controlled to afford spherical, worm-like and vesicular nano-objects, with free-standing gels being obtained over a broad range of PBzMA core-forming degrees of polymerisation (DPs). High monomer conversions (≥96%) were obtained within 2 hours for all PISA syntheses as determined by 1H NMR spectroscopy, and good control over molar mass was confirmed by gel permeation chromatography (GPC). Nanoparticle morphologies were identified using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and further detailed characterisation was conducted to monitor rheological, electrochemical and thermal characteristics of the nanoparticle dispersions to assess their potential in future electronic applications. Most importantly, this new PISA formulation in IL facilitates the in situ formation of worm ionogel electrolyte materials at copolymer concentrations >4% w/w via efficient and convenient synthesis routes without the need for organic co-solvents or post-polymerisation processing/purification. Moreover, we demonstrate that the worm ionogels developed in this work exhibit comparable electrochemical properties and thermal stability to that of the IL alone, showcasing their potential as gel electrolytes.

Publication DOI: https://doi.org/10.1039/D3SC06717C
Divisions: College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences > Aston Advanced Materials
College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > Aston Institute of Materials Research (AIMR)
College of Engineering & Physical Sciences > Aston Polymer Research Group
Funding Information: M. J. D. wishes to thank EPSRC for providing a DTP studentship for G. L. M. (EPSRC DTP 2020–2021, Aston University, Grant Ref: EP/T518128/1). M. J. D. also wishes to thank the Royal Society of Chemistry for support via a Research Enablement Grant (E20-007
Additional Information: Copyright © 2024 The Author(s). Published by the Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (https://creativecommons.org/licenses/by/3.0/).
Publication ISSN: 2041-6539
Data Access Statement: Data for this paper, including polymer and nanoparticle characterisation data, small-angle X-ray scattering fitting and models, oscillatory rheology data and electrochemical impedance spectroscopy data, are available in the ESI
Last Modified: 15 Jul 2024 08:31
Date Deposited: 19 Feb 2024 09:31
Full Text Link:
Related URLs: https://pubs.rs ... 4/sc/d3sc06717c (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2024-03-28
Published Online Date: 2024-02-13
Accepted Date: 2024-02-05
Authors: Maitland, Georgia Lucy
Liu, Mingyu
Neal, Thomas
Hammerton, James
Han, Yisong
Worrall, Stephen David (ORCID Profile 0000-0003-1969-3671)
Topham, Paul D. (ORCID Profile 0000-0003-4152-6976)
Derry, Matthew J. (ORCID Profile 0000-0001-5010-6725)

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