A systematic development of 2D alloy catalyst with synergistic performance of high lithium polysulfide (LiPS) binding energy and efficient Li+ ion/electron conduction is presented. The first section of work found that Li+ ions can flow through the percolated ion transport pathway in polycrystalline MoS2, while Na+ and K+ ions can easily flow through the percolated 1D ion channel near the grain boundaries. An unusually high ionic conductivity of extrinsic Li+, Na+, and K+ ions in 2D MoS2 film exceeding 1 S/cm was measured that is more than two orders of magnitude higher than those of conventional solid ionic materials, including 2D ionic materials. The second section of this dissertation focus on catalyzing the transformation of LiPSs to prevent the shuttle effect during the battery cycling by synthesizing 2H (semiconducting) – 1T (metallic) mixed phase 2D Mo0.5W0.5S2 alloy on CNF paper, using two step sputtering and sulfurization method. The lithium sulfur (Li-S) battery cell assembled with the 2D Mo0.5W0.5S2/CNF/S cathode shows a high specific capacity of 1228 mAh g-1 at 0.1C and much higher cyclic stability over 4 times as compared to the pristine cathodes. The high LiPSs binding energy of catalyst efficiently prevents the shuttling effect and corrosion of Li anode after long term stability test for over 400 cycles. The defect engineered MoWS catalyst on CNF showed significantly enhanced polysulfide transformation resulting in specific capacity of 1586 mAh g-1 at 0.05C for the full cell Li-S battery and much higher cyclic stability over 1000 cycles. Stacked layers of D-MoWS-CNF-S cathodes can result in an increased sulfur loading up to 10 mg cm-2 with highest achievable areal capacity of 13.5 mAh/cm2. The efficient sulfur utilization and reduced negative-to-positive capacity (N/P) ratio by D-MoWS catalyst significantly increased the gravimetric energy density to the highest reported value of 1090 Wh kg-1 w.r.t the total weight of anode and cathode.

Adsorption is a versatile purification technique to selectively separate different peptide fractions from a mixture using mild operation conditions. Porous carbons are ideally suited to separate ACE-inhibiting dipeptides by combining tailored size exclusion and polarity selectivity. The desired peptide fraction is mostly hydrophobic and very small and should adsorb inside hydrophobic micropores. The second topic of this thesis is linked to energy storage. The lithium-sulfur battery is a promising alternative to common lithium-ion batteries with theoretical capacities of up to 1672 mAh g−1 sulfur. The second aim of this thesis is to conduct an in-depth investigation of polysulfides interacting with selected carbon materials in a simplified battery electrolyte environment. The focus of this study is laid on the impact of surface polarity and pore size distribution of the carbon to develop a quantitative correlation between polysulfide retention and porosity metrics. Both, the enrichment of ACE-inhibitors and the retention of polysulfides rely on liquid phase adsorption in porous materials, linking the above mentioned topics. This thesis not only aims to develop an enrichment process or to find a superior battery cathode but also strives to explore structure-property relationships that are universally valid. Understanding the complex interplay of pore size and polarity leading to selective interactions between pore wall and the adsorbed species is given a high priority.

Les travaux presentés dans ce manuscrit ont été consacrés à l’étude de composés organo-soufrés comme composants d’électrolyte pour systèmes électrochimiques de stockage d’énergie, en particulier dans les batteries lithium-soufre. Des liquides ioniques originaux, basés sur des cations sulfonium fonctionnalisés par des chaînes de type glyme ont été synthétisés et caractérisés, puis testés en tant qu’électrolytes dans des supercondensateurs symétriques avec électrodes en carbone activé. Il est apparu que l’adaptation de la structure des liquides ioniques à la porosité du carbone activé est d’importance fondamentale pour le développement de systèmes plus performants. L’ étude menée sur les batteries lithium-soufre a permis une meilleure compréhension des mécanismes de fonctionnement d’un système redox soufre/diphenyl disulfure dans des solvants glymes. L’influence des solvants sur les équilibres chimiques entre polysulfures organiques et minéraux et sur le fonctionnement du système a été étudiée. D’après les premiers résultats obtenus, cette stratégie semble particulièrement prometteuse pour améliorer les performances des batteries lithium-soufre. / The work presented in this manuscript concentrates on investigating the use of organosulfur compounds as potential electrolyte components for electrochemical energy storage systems, in particular in lithium-sulfur batteries. Novel glyme-functionalised sulfonium-based ionic liquids were synthesised and characterised before being tested as pure electrolytes for symmetrical supercapacitors based on activated carbon electrodes. The adaptation of the structure of the ionic liquids to the porosity of activated carbon was found to be of fundamental importance for the design of more efficient systems. For lithium-sulfur batteries, the study has enabled a better understanding of the mechanisms involved during the operation of the sulfur/diphenyl disulfide redox couple in a range of glyme-based solvents. Similarly, the influence of the glyme-based solvents on the chemical equilibria between organic and mineral polysulfides and on the system operation has been investigated. The initial results demonstrated that this is a particularly promising strategy in order to significantly improve the performances of lithium-sulfur batteries.

The demand for electric vehicles is increasing rapidly as the world is preparing for a fossil fuel-free future in the automotive field. Lithium battery technologies are the most effective options to replace fossil fuels due to their higher energy densities. However, safety remains a major concern in using lithium as the anode, and the development of non-volatile, non-flammable, high conductivity electrolytes is of great importance. In this dissertation, a gel polymer electrolyte (GPE) consisting of ionic liquid, lithium salt, and a polymer has been developed for their application in lithium batteries. A comparative study between GPE and ionic liquid electrolyte (ILE) containing batteries shows a superior cyclic performance up to 5C rate and a better rate capability for 40 cycles for cells with GPE at room temperature. The improvement is attributed to GPE’s improved stability voltage window against lithium as well as higher lithium transference number. The performance of the GPE in lithium-sulfur battery system using sulfur-CNT cathodes shows superior rate capability for the GPE versus ILE for up to 1C rates. Also, GPE containing batteries had higher capacity retention versus ILE when cycled for 500 cycles vii at C/2 rate. Electrochemical impedance spectroscopy (EIS) studies reveal interfacial impedances for ILE containing batteries grew faster than in GPE batteries. The accumulation of insoluble Li2S2/Li2S on the electrodes decreases the active material thus contributes to capacity fading. SEM imaging of cycled cathodes reveals cracks on the surface of cathode recovered from ILE batteries. On the other hand, the improved electrochemical performance of GPE batteries indicates better and more stable passivation layer formation on the surface of the electrodes. Composite GPE (cGPE) containing micro glass fillers were studied to determine their electrochemical performance in Li batteries. GPE with 1 wt% micro fillers show superior rate capability for up to 7C and also cyclic stability for 300 cycles at C/2 rate. In situ, EIS also reveals a rapid increase in charge transfer resistance in GPE batteries, responsible for lowering the capacity during cycling. Improved ion transport properties due to ion-complex formations in the presence of the micro fillers, is evidenced by improved lithium transference number, ionic conduction, and ion-pair dissociation detected using Raman spectroscopy.

Une porosité hiérarchisée au sein de mousses solides permet la combinaison des avantages offerts par différentes échelles de structuration : les macropores offrent un grand volume poreux et une diffusion facilitée des réactifs, tandis que mésopores et micropores permettent confinement et grande surface spécifique. La chimie intégrative, en associant la matière molle et la chimie douce, dispose d’une variété de voies de synthèse pour obtenir de tels matériaux. Nous avons ainsi utilisé des émulsions et des tensioactifs comme empreintes pour la chimie sol-gel afin d’obtenir des mousses de silice présentant une porosité hiérarchisée. Elles ont ensuite été employées comme empreintes dures pour synthétiser des mousses de carbone, utilisées comme électrodes de batteries lithium-soufre présentant de grandes capacités. Nous avons ensuite étudié l’effet sur leurs performances de nanoparticules métalliques. Ces mousses ont également été testées pour le stockage de l’hydrogène, et nous avons montré un cyclage avec LiBH4 en présence de nanoparticules métalliques. Enfin, les mousses de silices ont été étudiées en tant que support pour la croissance bactérienne. En effet, lorsque des bactéries croissent dans un milieu confiné, leur cinétique de croissance et leur concentration finale peuvent être totalement différentes de ce qui est observé dans des cultures classiques, ce qui a un grand intérêt dans des domaines comme la biocatalyse. / Hierarchical porosity in solid foams allows the combination of the advantages offered by the different scales of structuration : macropores allow high porous volume and easy diffusion of reagents, while mesopores and micropores allow confinement and high specific surface areas. Integrative chemistry, associating soft matter and soft chemistry, offers a variety of synthetic pathways to generate such materials. We used emulsions and surfactants to template sol-gel chemistry in order to obtain silica foams bearing hierarchical porosity. These silica foams were employed as hard templates to synthesize carbon foams, used as electrodes in lithium-sulfur batteries bearing high capacities. We then explored the impact on performances of loading them with metallic nanoparticles. We also studied the potential of those carbon foams for hydrogen storage, and we obtained cycling capabilities with LiBH4 after loading them with metallic nanoparticles. Finally, the silica foams were used as a support for bacterial growth. Indeed, when bacteria grow in a confined medium, the kinetics of growth and their final concentration can be totally different than what is observed in classical cultures, which is of high interest for applications such as biocatalysis.

Les objectifs de ce travail de thèse étaient d’explorer de nouvelles voies pour l’amélioration des performances des accumulateurs Li/S, systèmes présentant de fortes densités d’énergie théorique dont les performances sont limitées par un mécanisme électrochimique incluant des intermédiaires solubles et réactifs. Ces intermédiaires induisent une faible efficacité coulombique et une perte importante de capacité au cours du cyclage. Plusieurs stratégies ont été mises en place pour créer une barrière de nature organique, au transport ou à la réactivité de ces polysulfures, tout en gardant une approche versatile et simple à mettre en œuvre. De bons résultats ont été obtenus en termes d’efficacité coulombique et de cyclabilité, notamment grâce à l’utilisation d’un matériau polymère capable d’interactions ioniques avec les intermédiaires soufrés. Le mécanisme de dépôt du lithium et de croissance dendritique a été également étudié, pour une compréhension plus complète du système. / The objectives of this thesis work were to explore new strategies to improve the performance of Li / S accumulators, systems exhibit with high theoretical energy densities whose performance is limited by an electrochemical mechanism including soluble and reactive intermediates. These intermediates induce a low coulombic efficiency and a significant loss of capacity during cycling. Several strategies have been evaluated to create a barrier of organic nature, which mitigate the transport or the reactivity of these polysulfides. The solutions explored are versatile and simple to implement. Good results have been obtained in terms of coulombic efficiency and cyclability, in particular through the use of a polymeric material enables to form ionic interactions with the sulfur intermediates. The mechanism of lithium deposition and dendritic growth has also been studied, for a more complete understanding of the system.

Die vorliegende Arbeit liefert einen Beitrag für ein besseres Verständnis über die zyklische Alterung von Siliciumnanopartikel (Si-NP) als Anodenmaterial in Lithium-Ionen- und Lithium-Schwefel-Batterien. Im Fokus der Studie stand der Einfluss der Partikelgröße, des Elektrodendesigns und der Elektrolytzusammensetzung auf die elektrochemische Reversibilität des Siliciums zur Lithiumspeicherung. Über umfangreiche strukturelle Charakterisierungstechniken mittels Röntgenbeugung, Elektronenmikroskopie und der Röntgenphotoelektronenspektroskopie in Verbindung mit elektrochemischen Untersuchungsmethoden, konnten wesentliche Mechanismen zur Degradation aufgeklärt und die Funktion diverser Oberflächenverbindungen auf der Siliciumanode identifiziert werden. Als Hauptursache der Degradation von Si-NP mit einer Partikelgröße unter 20 nm konnte das Wachstum der Solid-Electrolyte-Interface (SEI) identifiziert werden. Pulverisierung und die Bildung neuer kristalliner Phasen kann ausgeschlossen werden. Es wurde ein kostengünstiges und flexibles Verfahren zur Herstellung eines nanostrukturierten Silicium-Kohlenstoff-Komposites entwickelt, welches unter optimierten Bedingungen eine spezifische Kapazität von 1280 mAh/g(Elektrode) und einen Kapazitätserhalt von 81 % über 500 Tiefentladungszyklen liefert. Es konnten erfolgreich hoch reversible Flächenkapazitäten von 5 mAh/cm^2 bei nur 4,4 mg/cm^2 Elektrodengewicht nachgewiesen werden. Für die Arbeit wurde zunächst ein Verfahren zur Herstellung von monodispersen Si-NP mit einer Größe von 5 nm – 20 nm angewendet. Die galvanostatische Zyklierung gegen Lithiummetall hat ergeben, dass mit abnehmender Partikelgröße die Reversibilität des Siliciums zunimmt. Über in situ Synchrotron XRD und post mortem XPS konnte eine stabilere Solid-Electrolyte-Interface (SEI) mit abnehmender Partikelgröße als Hauptursache identifiziert werden. Im weiteren Verlauf der Arbeit wurden Si-NP im porösen Kohlenstoffgerüst durch ein leicht modifiziertes Herstellungsverfahren abgeschieden und untersucht. Durch das veränderte Elektrodendesign konnte die Reversibilität bei gleichem Kohlenstoffgehalt deutlich verbessert werden, da der Kontaktverlust des Siliciums zum leitfähigen Gerüst durch SEI Wachstum verzögert wird. Die Elektrolytadditive Fluoroethylencarbonat und Vinylencarbonat führen zu einer weiteren Verbesserung der Reversibilität, wobei Vinylencarbonat die höchste Reversibilität zur Folge hat, jedoch einen hohen Filmwiderstand verursacht. Weiterhin wurden etherbasierte Elektrolyte, welche typischerweise in Lithium-Schwefel-Batterien zum Einsatz kommen, untersucht. Hierbei wurde eine positive Wirkung von Lithiumnitrat auf die Reversibilität von Silicium festgestellt. Es konnten erfolgreich Si-Li-S (SLS) Vollzellen getestet werden, welche eine höhere Lebensdauer als vergleichbare Zellen mit Lithiummetall als Anode aufweisen. Aus den elektrochemischen und post mortem Untersuchungen konnte ein positiver Einfluss von Polysulfiden auf die SEI von Silicium nachgewiesen werden. Durch die umfangreichen post mortem Analysen konnte die Funktion diverser, in der SEI des Siliciums auftretender Verbindungen in Abhängigkeit der Elektrolytzusammensetzung aufgeklärt werden. Es wurde ein anschaulicher Mechanismus des SEI Wachstums in Abhängigkeit des Elektrolyts erstellt. / The results of this work provide a better understanding about the cyclic aging of silicon nanoparticles (Si-NP) as anode material in Lithium-ion- and Lithium-sulfur batteries. Subject of investigation was the influence of particle size, electrode design and electrolyte composition on the electrochemical reversibility of Si-NP for lithium storage. The main characterization techniques used in this study were XRD, SEM, TEM and XPS combined with electrochemical analysis and in situ synchrotron XRD. Bare silicon nanoparticles ranging from 5 – 20 nm and silicon nanoparticles embedded within a porous carbon scaffold were prepared through a cost-effective and novel synthesis technique including the hydrolysis of trichlorosilane as feedstock. The dominant degradation mechanism of these silicon nanoparticles was identified to be the continuous growth the solid-electrolyte-interphase (SEI). Other phenomena such as pulverisation or new evolving crystalline phases are excluded. It was found that a reduction of the particle size from 20 nm to 5 nm increases the reversibility due to a thicker and therewith more stable SEI. The deposition of the silicon nanoparticles into a porous carbon scaffold caused a significant improvement of the reversibility at constant carbon content. The effect of the electrolyte additives Fluoroethylene carbonate and Vinylene carbonate was analysed in detail. Furthermore, typical electrolyte compositions used for lithium-sulfur-batteries were tested and studied. Si-Li-S (SLS) full cells were demonstrated which outperform conventional lithium-sulfur batteries in terms of life time. The systematic analysis and the rational optimization process of the particle size, electrode design and electrolyte composition allowed to provide a nanostructured silicon electrode with a specific capacity of up to 1280 mAh/g(Electrode) and 81 % capacity retention after 500 deep discharge cycles. Reversible areal capacities of 5 mAh/cm^2 at 4.4 mg/cm^2 electrode weight were demonstrated.