As technologies grow towards more demanding and complex applications, energy and environmental sectors carry a relevant fraction of the ecological burden for the next generations to come. Renewable energies, efficient industrial processes and clever management of environmental resources must be taken into serious account to reduce as much as possible our footprint. In this scenario, material science aims at finding solution for the most disparate scientific issues, these including the synthesis of multifunctional and performing materials able to fill the gap with innovative and green technologies. Among others, ceramic materials have shown a growing flexibility towards green and functional applications also thanks to the Polymer-Derived Ceramic route (PDC). This pathway to ceramic materials has the advantage of controlling their composition at the molecular level via chemical reactions, thus permitting to obtain complex ceramic systems with particular functionalities after controlled pyrolysis of preceramic polymers. Besides, Polymer-Derived Ceramic routes can be implemented with many processing solutions, such as the outgrowing fields of 3D printing and ceramic matrix composites. Among these, porous and cellular ceramics can be synthesized via PDC routes as well, laying the foundations for new, cheap and functional sorbents and scaffolds. In such a scenario, ceramic aerogels are ultraporous materials possessing high surface areas, low density and pore size distributions that easily reach few nanometers while maintaining rather high porosities, generally above 90%. Hence, when compared with other porous ceramics, aerogels present outperforming microstructural features that make them intriguing for applications in the energy and environmental fields, and when the PDC route is combined with aerogels processing, the outcome is something new. This thesis deals exactly with these two concepts, in the framework of innovative energy storage and environmental pollution mitigation. As a matter of fact, this work offers novel synthesis pathways for PDC ceramic aerogels belonging to the Si-C-N-O system, where their chemistry and microstructure have been tuned to serve for the abovementioned applications. Particular attention has been devoted to Si-N, Si-C-N, Si-C and Si-O-C aerogels, characterizing their thermal evolution when changing polymeric precursors and synthesis parameters. On this point, perhydropolysilazane (PHPS) and Durazane® 1800 were employed as precursors for silicon nitride and carbonitride aerogels, SPR-036 and polymethylhydrosiloxane (PHMS) as precursors for SiOC, and SMP-10 polycarbosilane as starting point for producing SiC aerogels. Our interest in making of these aerogels lies both on the urge of understanding the principles behind their synthesis steps, how each of them has an impact on the final aerogel chemistry, microstructure and thermal stability, and given this, how processing parameters can be exploited for novel applications of such peculiar materials. Overall, this thesis offers a paper collection of these novel aerogels featuring applications such as thermal and thermochemical energy storage, thermal insulation, electrochemistry and polluted water management, where we demonstrate the versatility and the potential of PDC routes towards the synthesis of ultraporous functional ceramics.

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Gurpreet Singh / The inevitable depletion of fossil fuels and related environmental issues has led to exploration of alternative energy sources and storage technologies. Among various energy storage technologies, rechargeable metal-ion batteries (MIB) are at the forefront. One dominant factor affecting the performance of MIB is the choice of electrode material. This thesis reports synthesis of paper like electrodes composed for three representative layered materials (van der Waals sheets) namely reduced graphene oxide (rGO), molybdenum disulfide (MoS₂) and hexagonal boron nitride (BN) and their use as a flexible negative electrode for Li and Na-ion batteries. Additionally, layered or sandwiched structures of vdW sheets with precursor-derived ceramics (PDCs) were explored as high C-rate electrode materials. Electrochemical performance of rGO paper electrodes depended upon its reduction temperature, with maximum Li charge capacity of 325 mAh.g⁻¹ observed for specimen annealed at 900°C. However, a sharp decline in Na charge capacity was noted for rGO annealed above 500 °C. More importantly, annealing of GO in NH₃ at 500 °C showed negligible cyclability for Na-ions while there was improvement in electrode's Li-ion cycling performance. This is due to increased level of ordering in graphene sheets and decreased interlayer spacing with increasing annealing temperatures in Ar or reduction at moderate temperatures in NH₃. Further enhancement in rGO electrodes was achieved by interfacing exfoliated MoS₂ with rGO in 8:2 wt. ratios. Such papers showed good Na cycling ability with charge capacity of approx. 225.mAh.g⁻¹ and coulombic efficiency reaching 99%. Composite paper electrode of rGO and silicon oxycarbide SiOC (a type of PDC) was tested as high power-high energy anode material. Owing to this unique structure, the SiOC/rGO composite electrode exhibited stable Li-ion charge capacity of 543.mAh.g⁻¹ at 2400 mA.g⁻¹ with nearly 100% average cycling efficiency. Further, mechanical characterization of composite papers revealed difference in fracture mechanism between rGO and 60SiOC composite freestanding paper. This work demonstrates the first high power density silicon based PDC/rGO composite with high cyclic stability. Composite paper electrodes of exfoliated MoS₂ sheets and silicon carbonitride (another type of PDC material) were prepared by chemical interfacing of MoS₂ with polysilazane followed by pyrolysis . Microscopic and spectroscopic techniques confirmed ceramization of polymer to ceramic phase on surfaces on MoS₂. The electrode showed classical three-phase behavior characteristics of a conversion reaction. Excellent C-rate performance and Li capacity of 530 mAh.g⁻¹ which is approximately 3 times higher than bulk MoS₂ was observed. Composite papers of BN sheets with SiCN (SiCN/BN) showed improved electrical conductivity, high-temperature oxidation resistance (at 1000 °C), and high electrochemical activity (~517 mAh g⁻¹ at 100 mA g⁻¹) toward Li-ions generally not observed in SiCN or B-doped SiCN. Chemical characterization of the composite suggests increased free-carbon content in the SiCN phase, which may have exceeded the percolation limit, leading to the improved conductivity and Li-reversible capacity. The novel approach to synthesis of van der Waals sheets and its PDC composites along with battery cyclic performance testing offers a starting point to further explore the cyclic performance of other van der Waals sheets functionalized with various other PDC chemistries.

Les matériaux céramiques se sont énormément développés durant le dernier siècle et ne cessent d'attirer l'attention pour diverses applications. Cela tient aux propriétés nombreuses et variées qu'elles peuvent présentées. Un avantage certain de ce type de matériaux réside dans leurs stabilités mécanique, thermique et chimique, ce qui en fait des candidats de choix pour des applications dans des environnements sévères. Ceci est notamment observable dans le domaine des membranes. En effet, malgré leurs coût réduit, les membranes polymères, constituant l'essentiel des membranes utilisées à ce jour, sont très sensibles à l'environnement dans lequel elles sont utilisées et nécessitent d'être renouvelées régulièrement. Cela justifie la recherche d'alternatives, comme par exemple les céramiques plus résistantes. Différentes mises en forme sont possibles pour la formation de membranes, mais parmi celles-ci, les formes en tubes ont suscité un engouement certain en raison des avantages en termes de rapport surface/volume et de la résistance au transport de masse moindre. La majorité des céramiques utilisées et commercialisées reposent sur des compositions chimiques à base d'oxydes. Il apparaît cependant que ces matériaux trouvent leurs limites en termes de vieillissement et de stabilité à très haute température. Un autre type de céramiques, les céramiques non-oxydes à base de silicium, présentent des propriétés très intéressantes, pouvant potentiellement répondre à ces problématiques. De tels matériaux sont produits par la voie PDC (Polymer Derived Ceramic), notamment en raison de l'impossibilité de procéder autrement pour la majorité d'entre eux. Cette méthode consiste à synthétiser des polymères pré-céramiques pouvant être convertis en céramiques par un traitement thermique adéquat. Cela permet notamment un très bon contrôle de la structure chimique de la céramique finale, et donc une grande versatilité. Parmi ces matériaux, le système quaternaire Si-B-C-N a particulièrement attiré l'attention en raison de ses propriétés thermostructurales couplées à sa stabilité chimique singulière. Les travaux de thèses présents se sont donc focalisés sur l'utilisation de cette céramique. Un autre avantage de la voie des polymères pré-céramiques réside dans les mises en forme rendues possibles par l'utilisation de polymères. Cette méthode a déjà été utilisée abondamment pour produire des fibres céramiques avec des diamètres de l'ordre de la dizaine de microns, notamment par le recours à la technique de filage en fondu (melt-spinning en anglais). L'objectif principal de cette thèse est la production de fibres creuses et de capillaires céramiques SiBCN en se basant sur cette méthode de mise en forme. Le but est la formation de supports membranaires très stables à un coût relativement faible comparé aux procédés généralement utilisés pour la mise en forme de céramiques, impliquant souvent un traitement de frittage à très haute température. Ces supports offriront à terme des applications en séparation de gaz ou en traitement de l'eau. Plus exactement, le chapitre 1 concerne l'état de l'art et permet de présenter le contexte de ces travaux, ainsi que leur intérêt. Le chapitre 2 présente les techniques de synthèses mises en œuvre et les matériaux utilisés. Le chapitre 3 est consacré à la production de fibres creuses céramiques SiBCN en présentant notamment une étude complète de la structure chimique du polymère utilisé, ainsi que l'évolution de la microstructure de la céramique résultante à haute température. Le chapitre 4 a pour objet la formation de capillaires céramiques SiBCN. Ici aussi, le précurseur utilisé est caractérisé en détail, de même que la céramique issue de sa pyrolyse. Le dernier chapitre consiste en une ouverture et propose différentes méthodes de modification de surface des fibres creuses et des capillaires élaborés dans les chapitres 3 et 4. / New ceramic materials have progressively emerged during the last century and continuously drew attention for diverse applications. This comes from the numerous and various properties they can exhibit. A great advantage of this type of materials is their mechanical, thermal and chemical stabilities, that makes ceramics of great interest for applications in harsh environments. This trend is especially perceptible in the field of membranes. In fact, despite their moderate cost, polymer membranes, which are mostly used, are very sensitive to the environment in which they are used and require to be replaced regularly. This justifies the search for alternatives and for more resistant materials like ceramics. Various shaping are possible to build a membrane, but among these, shapings in form of tubes have aroused particular enthusiasm because of their advantages in terms of surface/volume ratio and of lower mass transport resistance. Most of used and commercialized ceramics are based on oxide chemical compositions. This constitutes a drawback concerning the aging of the membranes and their stability at very high temperatures. Another type of ceramics, non oxide silicon based ceramics, exhibits very interesting properties which could eventually palliate these problems. In general, such materials are produced through the PDC route (Polymer Derived Ceramic route), especially because of the impossibility to proceed by more conventional methods for many of them. The principle of this bottom-up method is to synthesize preceramic polymers which can be converted into ceramics through an appropriate heat treatment. This enables a very good control of the chemical structure of the final ceramics and so a great versatility. Among these materials, the quaternary system Si-B-C-N has aroused big interest because of its extraordinary thermostructural properties coupled to chemical inertness. Thus, the present work has been focused on the preparation and application of this ceramic. Another advantage of the PDC route can be found in the possible shaping arising from the polymeric nature of the precursors. This method has been widely used for the production of thin ceramic fibers by using the melt-spinning process. The main objective of this thesis is the design of SiBCN ceramic hollow fibers and capillaries based on this shaping method. The aim is the preparation of very stable membrane supports at relatively low costs compared to conventional processes used to shape ceramic materials, often involving a sintering treatment at a very high temperature. These supports could be used in gas separation and water treatment applications. More precisely, chapter 1 presents a state of the art and allows to give the context and the motivations of this work. Chapter 2 discusses on the synthesis techniques and on the used methods. Chapter 3 is dedicated to the production of SiBCN ceramic hollow fibers by studying in details the precursors chemical structure used for this purpose before investigating its ceramic conversion and the evolution of the microstructure of the resulting ceramic. Chapter 4 is dealing with the production of SiBCN ceramic capillaries. The precursor used is characterized as well as the resulting ceramic. The last chapter gives some perspectives by proposing different methods of surface modifications of the hollow fibers and the capillaries presented in chapters 3 and 4.

Traditional Lithium-Ion Batteries (LIBs) are a reliable and cost-efficient choice for energy storage. LIBs offer high energy density and low self-discharge. Recent developments in electric-based technologies push for replacing historically used Lead-Acid batteries with LIBs. However, LIBs do not yet meet the demands of modern technology. Silicon and graphene oxide (GO) have been identified as promising replacements to improve anode materials. Graphene oxide has a unique sheet-like structure that provides a mechanically stable, light weight material for LIB anodes. Due to its structure, reduced graphene oxide (rGO) is efficiently conductive and resistive to environmental changes. On the other hand, silicon-based anode materials offer the highest theoretical energy density and a high Li-ion loading capacity of various elements [20]. Silicon-based anodes that have previously been studied demonstrated extreme volumetric expansion over long cycles due to lithiation. Polysiloxane may be an interesting alternative as it is a Si-based material that can retain the high Li-ion loading capacity of Si while lacking the unattractive volumetric expansions of Si. Polymer derived ceramic-decorated graphene oxide anodes have been suggested to increase loading capacity, thermal resistance, power density, and mechanical stability of LIBs. Coupled with mechanically stable graphene oxide, polymer derived ceramic nanoparticle decorated graphene oxide anodes are studied to establish their efficiencies under operating conditions.