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Hélène Pung

Thermotropic Ionic Liquid Crystals: Structure/Ionic transport properties relationships

Published on 15 March 2024
Thesis presented March 15, 2024

Developing multi-scale spatial (nano/meso/micro-macroscopic) and temporal studies is crucial to understand, control, and pilot the relationships linking the structure to the ionic transport properties of hierarchically self-assembled functional materials. It is along these research lines that this exploratory work is positioned to meet their associated scientific challenges. It aims in particular to bring together elements of understanding for designing families of electrolytes with tunable-by-design (cat/an)ionic conductivity levels and that can be implemented by reliable manufacturing processes to authorize their scalable integration into more efficient electrochemical energy conversion and storage devices. The scrutinized model families of soft-matter electrolytes are Thermotropic Ionic Liquid Crystals (TILCs), which synergistically combine dynamic hierarchical self-assembly with self-healing functionalities to encode dimensionality (quasi-1D/ quasi-2D/3D) controlled ionic transport. This research work presents and discusses the molecular engineering, syntheses and detailed studies of these model stimuli-responsive (An/Cat)ionic (A/C)-TILCs conductors.
The study of the supramolecular organization of a model family of K+ and Na+ cation-conducting C-TILCs has unraveled i) a monotropic (i.e. which develops only during of the first heating scan) bicontinuous​ Cubic mesophase (Cubbi) with an Ia3d symmetry and ii) a hexagonal Columnar mesophase (Colhex), encoding 3D and quasi-1D transport processes, respectively. Polar ionic sub-domains are localized at the heart of the columns decorated at their periphery by aliphatic chains. The experimental study and modelling of the confinement of charge carriers within a model family of C18C18Im+/X- (X= Br-, I-, N(CN)2-) A-TILCs forming interdigitated Smectic A mesophases (SmAd are hosting quasi-2D anisotropic ionic transport) reveals a regime of nanoconfinement of anions subjected to electrostatic interactions within the ca. 1 nm-"thick" polar sub-layers within their lamellar organizations. The study of these TILCs thus addresses the functional impact of mosaicity, i.e. how the coexistence of mesomorphic domains presenting different orientations and sizes is impacting ionic transport. A first direct experimental description allows to describe the role of this dynamic mosaicity both i) on the long-range organization of mesomorphic domains and ii) onto ion transport at the meso-/macro-scopic scale. Within mesophases formed by the K+-cation conducting C-TILC, the Cubbi mesophase presents conductivity values two orders of magnitude greater than those associated to the Colhex mesophase. As the Cubbi mesophase does not require specific defect management strategies (low density of defects/homophasic interfaces), it turns out that polar subdomains can thus percolate efficiently according to an intrinsically 3D mechanism. In contrast, the long-range ordering of the (dynamic) SmAd mesomorphic domains of the C18C18Im+/N(CN)2- A-TILC, induced by the application of an external stimulus (here, a magnetic field of 1 T), results in a ca. x1.6 increase (from 92 to 145 nm) of the average size of mesomorphic domains at 80°C. Due to the reduction of the disorder and of the number of homophasic interfaces (which can penalize the transport of anions), a natural (expected) increase in conductivity values by a factor ca. x2.6 (9 to 25 µS·cm-1) is observed. Ultimately, TILCs, i.e. 2.0 electrolytic materials encoding ionic transport properties and (bioinspired) dynamic self-assembly/repairing functionalities, are consisting in an original class of stimuli-sensitive functional materials for the electrochemical conversion and storage of energy.

Organic chemistry, Thermotropic Ionic Liquid Crystals (TILCs), Dynamic hierarchical self-assembly, Bioinspired stimuli-responsive organic electrolytes, Multiscale structure/ionic transport properties correlations, Electrochemical energy storage