Maximilien CORONAS
a soutenu sa thèse de doctorat
le 16 décembre 2025
Manufacturing of nanostructured hybrid membranes by self-assembly of block copolymer with addition of inorganic compounds
In front of the jury composed of:
– Marie-Vanessa COULET, Directrice de recherches au CNRS, Université Aix-Marseille – Rapporteur
– Guillaume FLEURY, Professeur des Universités, Université de Bordeaux – Rapporteur
– Sophie TINGRY, Directrice de recherches au CNRS, Université de Montpellier – Examinateur
– Xavier CATTOEN, Chargé de recherches au CNRS, Université de Grenoble – Examinateur
– Julien CAMBEDOUZOU, Professeur des Universités, Université de Montpellier – Directeur de thèse
– Karim AISSOU, Chargé de recherches au CNRS, Université de Montpellier – Co-encadrant de thèse
Abstract:
Nanostructured hybrid membranes represent a particularly promising approach for the design of next-generation solid electrolytes for both lithium-ion batteries and fuel cells, thanks to the spatial decoupling of ionic conduction properties and mechanical properties. In the field of fuel cells, for example, these nanostructured hybrid membranes could promote the development of anion exchange membranes (AEMs) capable of combining high ionic conductivity with increased mechanical stability, achieved through the infiltration of inorganic precursors. This performance is based on the engineering of hydrophilic ion-conducting nanochannels, continuous throughout the entire thickness of the AEM, which ensure efficient ion transport within a stable and robust hydrophobic matrix.
In order to assess the feasibility of such solid electrolytes, this thesis work consisted of developing nanostructured AEMs based on block copolymer chains (BCPs), whose robustness was enhanced by incorporating inorganic precursors into the material. To do this, the inorganic precursor was either directly incorporated into the BCP chains during their synthesis (e.g., poly(1,1-dimethylsilacyclobutane)-block-polystyrene-block-poly(methyl methacrylate), PDMSB-b-PS-b-PMMA), or infiltrated in liquid phase (LPI) or vapor phase (VPI) into polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) (PS-b-P2VP-b-PEO) films after their shaping. In the latter case, three inorganic precursors were used – tetraethoxysilane (TEOS), triethoxymethylsilane (TEMS), and 3‑iodopropyltrimethoxysilane (IPTMS) – for the preparation of nanostructured hybrid membranes.
Remarkably, nanostructured hybrid membranes based on PS-b-P2VP-b-PEO with superior mechanical properties were obtained by applying solvent vapor annealing, leading to the formation of channels arranged in a gyroid phase, and then incorporating inorganic precursors (in particular IPTMS) by VPI. The reactivity of IPTMS with the P2VP block made it possible to generate AEMs carrying pyridinium-type cations. The impact of the structural morphology of the nanochannels (which evolves with the exposure time of the BCP chains to dichloromethane vapor) and the rate of IPTMS incorporation on the mechanical properties and ionic conductivity of the AEMs was studied by dynamic mechanical analysis and electrochemical impedance spectroscopy.
Keywords: Solvent vapor annealing, hybrid anion exchange membrane, block copolymer self‑assembly, gyroid, ionic conductivity.
