L’intégration des supercondensateurs dans les applications de type véhicule hybride nécessite la connaissance de leur comportement au cours du vieillissement. Ainsi, l’objectif de cette thèse est l’évaluation du vieillissement et la définition d’un modèle permettant la prédiction de l’état de santé des supercondensateurs. Les résultats de vieillissement sont présentés en s’intéressant principalement à l’évolution des performances durant le vieillissement accéléré en fonction de la température, de la tension et de la durée des arrêts dans le cas du cyclage. Un modèle de vieillissement est défini pour décrire l’évolution des performances en s’attachant aux principaux mécanismes de vieillissement. / The integration of ultracapacitors in applications like hybrid requires knowledge of their behavior during aging. Thus, the objective of this thesis is the evaluation of aging and the definition of a model for predicting the health of supercapacitors. The aging results are presented focusing mainly on the evolution of performance during accelerated aging function of temperature, voltage and duration of stops in the case of cycling. An aging model is defined to describe the evolution of performance by focusing on the key mechanisms of aging.

Abstract The main objectives of this thesis are to synthesize macroscopic well-aligned multi-walled carbon nanotube films and, based on their electrical conductivity, porosity and structural uniformity, highlight potential applications for further development. In this thesis, catalytic chemical vapour deposition from ferrocene-xylene precursors is optimized to grow high quality films of long, aligned multi-walled carbon nanotubes on lithographically patterned templates in high (~800ºC) temperatures. The impacts of reaction time, temperature and precursor concentration on MWCNT film quality (film thickness, purity, density and nanotube diameter distribution) are studied. Because of the excellent control of growth selectivity and film thickness inherent to the method, several interesting applications, including solar cell and capacitor electrodes, contact brushes, coolers, particulate filters and catalyst membranes, have been developed for nanotube films in collaboration between Finnish and international research groups over the past few years. In this thesis, advanced capacitor electrodes with improved charge storage and efficient particulate filters are discussed in closer detail. As the high temperatures used for growing high quality carbon nanotubes often cause complications in cases where nanotubes need to be directly integrated with other materials, experiments were also conducted with the aim of making the growth temperature as low as possible. After testing several catalyst and precursor combinations, cobalt nanoparticles deposited on silica surfaces were found to form carbon nanotubes from vaporized cyclopentene oxide precursor already at 470°C. The results show that catalytic chemical vapour deposition is a feasible and versatile method that can be combined with photolithography to produce multi-walled carbon nanotube films with desired footprint area and thickness on various substrates. The demonstrated new applications and technical solutions are expected to contribute to further development leading to competitive practical devices based on carbon nanotubes. / Tiivistelmä Tämän väitöstyön päätavoitteina ovat makroskooppisten, yhdensuuntaisista moniseinämäisistä hiilinanoputkista koostuvien kalvojen valmistaminen ja sovellutusten esittäminen perustuen kalvojen sähkönjohtavuuteen, huokoisuuten ja rakenteelliseen yhdenmukaisuuteen. Katalyyttis-kemiallinen höyryfaasikasvatusmenetelmä on optimoitu korkealaatuisten, yhdensuuntaisista, pitkistä moniseinämäisistä hiilinanoputkista koostuvien kalvojen tuottamiseen korkeissa lämpötiloissa (~800ºC) fotolitografialla kuvioiduille kasvualustoille käyttäen ferroseeni/ksyleeni-lähtöainetta. Reaktioajan, lämpötilan ja lähtöainepitoisuuden vaikutusta nanoputkikalvon laatuun on tutkittu tarkastelemalla kalvon paksuutta, puhtautta, tiheyttä ja nanoputkien läpimittajakaumaa. Erinomaisen kasvuselektiivisyyden ja kalvon paksuuden kontrolloimisen ansiosta nanoputkikalvoja voidaan räätälöidä useisiin mielenkiintoisiin sovellutuksiin (esim. aurinkokennot ja kondensaattorin elektrodit, hiiliharjat, jäähdyttimet, partikkelisuodattimet ja katalyyttikalvot), joita olemme kehittäneet viime vuosina yhdessä suomalaisten ja kansainvälisten tutkimusryhmien kanssa. Tässä väitöstyössä on tarkasteltu lähemmin uudentyyppisiä kondensaattorielektrodeja, joilla on parantunut sähkövarauksen varastointikyky, sekä tehokkaita partikkelisuodattimia. Hiilinanoputkien kasvattaminen korkeissa lämpötiloissa aiheuttaa usein ongelmia integroitaessa nanoputkia toisiin materiaaleihin. Tästä johtuen tutkimuksessa pyrittiin saamaan nanoputkien kasvatuslämpötila mahdollisimman alhaiseksi testaamalla useita lähtöaine-katalyytti-kombinaatioita, joista koboltti-nanopartikkelit piidioksidin päällä ja syklopenteenioksidi lähtöaineena muodostivat hiilinanoputkia jo 470°C:ssa. Tulosten perusteella katalyyttis-kemiallinen höyryfaasikasvatusmenetelmä yhdistettynä fotolitografiaan on hyvin monipuolinen tapa tuottaa moniseinämäisiä hiilinanoputkia halutulla kuviolla ja kalvonpaksuudella erilaisille substraateille. Tässä väitöstyössä demonstroitujen uusien sovellutusten ja teknisten ratkaisujen odotetaan johtavan uusiin, hiilinanoputkiin perustuviin kilpailukykyisiin käytännön laitteisiin.

Philosophiae Doctor - PhD

With the discovery of conductivity in doped polyacetylene (PA), a new era in synthetic metals has emerged by breaking the traditionally accepted view that polymers were always insulating. Conducting polymers are essentially characterized by the presence of conjugated bonding on the polymeric back bone, which facilitates the formation of polarons and bipolarons as charge carriers. Among the numerous conducting polymers synthesized to date, polypyrrole (PPy) is by far the most extensively studied because of prodigious number of applications owing to its facile polymerizability, environmental stability, high electrical conductivity, biocompatibility, and redox state dependent physico-chemical properties. Electrochemically prepared PPy is more interesting than the chemically prepared polymer because it adheres to the electrode surface and can be directly used for applications such as supercapacitors, electrochemical sensors, electromechanical actuators and drug delivery systems. In quest for improvement in quality of the device performances in the mentioned applications, micro and nano structured polymeric materials which bring in large surface area are studied. Finding a simple and efficient method of synthesis is very important for producing devices of PPy microstructures. Till date, Hard and soft template methods are the most employed methods for synthesis of these structures. Soft template based electrochemical methods are better than hard template methods to grow clean PPy microstructures on electrode substrates as procedures for removal of hard templates after the growth of microstructures are very complex. As per the literature, there is no unique method available to grow PPy microstructures which can demonstrate several applications. Although gas bubble based soft template methods are exploited to grow conducting polymer microstructures of sizes in few hundreds of micrometers, studies on applications of the same are limited. Hence it is planned to develop procedures to grow microstructures that can be used in several applications. In the current work, PPy microstructures with high coverage densities are synthesized on various electrode substrates by soft template based electrochemical techniques. Hollow, hemispherical and spherical PPy microstructures are developed by a two step method using electro generated hydrogen bubble templates on SS 304 electrodes. In the first step, Hydrogen bubbles are electro generated and stabilized on the electrode in the presence of β- naphthalene sulfonic acid (β-NSA). In the second step, Pyrrole is oxidised over the bubble template to form PPy microstructures. Microstructures (open and closed cups) of average size 15 μm are uniformly spread on the surface with a coverage density of 2.5×105 units /cm2. Globular PPy microstructures are developed by a single step method using concomitantly electro generated oxygen bubble templates on SS 304 electrodes during electropolymerization. Microstructures of average size 4 μm are uniformly spread on the surface with a coverage density of 7×105 units/cm2. Surfactant properties of Zwitterionic 4-(2-hydroxyethyl)-1-piperazine ethane sulfonic acid (HEPES) are exploited for the first time to grow conducting polymer microstructures. Ramekin shaped PPy microstructures are developed using HEPES as the surfactant to stabilize hydrogen bubble templates in a two step electrochemical synthesis method. Microramekins of size 100 µm are uniformly spread on the surface with a coverage density of 3000 units/cm2. Micropipettes and microhorns of PPy are synthesised by a single step electrochemical route using HEPES as a surfactant. Hollow micropipettes of length 7 µm with an opening of 200 nm at the top of the structure are observed. Similarly microhorn/celia structures are observed with length 10-15 µm. Microcelia are uniformly distributed over the surface with each structure having a diameter of 2 µm at the base to 150 nm at the tip. Growth mechanism based on contact angle of the reactant solution droplets on the substrate is proposed. PPy microstructures are characterized by scanning electron microscopy, X-Ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman Spectroscopy and UV-Visible spectroscopy to study morphology, ‘chemical bonding and structure’ , ‘defects and charge carriers’. Applicability of the electrodes with PPy microstructures in supercapacitors is investigated by cyclic voltammetry, chronopotentiometry and electrical impedance spectroscopy. Electrodes developed by all the above methods demonstrated very good supercapacitance properties. Supercapacitor studies revealed very high specific capacitances (580, 915, 728 and 922 F/g,) and specific powers (20, 25, 13.89 and 15.91 kW/kg) for electrodes with PPy microstructures (H2 bubble based two step method, O2 bubble based single step method, HEPES stabilized H2 bubbble method and HEPES based microhorn/celia structures respectively). Supercapacitive behavior of all the electrodes is retained even after an extended charge-discharge cycling in excess of 1500 cycles. Horseradish peroxidase entrapped, bowl shaped PPy microstructures are developed for H2O2 biosensing. Amperometric biosensor has a performance comparable to the sensors reported in the literature with high sensitivity value of 12.8 μA/(cm2.mM) in the range 1.0 mM to 10 mM. Glucose oxidase entrapped PPy amperometric biosensor is developed for Glucose sensing. Sensitivity of 1.29 mA/(cm2.mM) is observed for β-D-Glucose sensing in the 0.1 mM to 5.0 mM range while 58 μA/(cm2.mM) is observed in the 5.0 to 40 mM range. Potentiometric urea sensor with urease entrapped PPy microstructures on SS electrode is developed. It is able to sense urea in the micromolar ranges down to 0.1 μM. It represented an excellent performance with sensitivity of 27 mV/decade. Sensitivity in the micromolar range is 4.9 mV/(μM.cm2). Drug encapsulation and delivery is successfully demonstrated by two actuation means (i) by electrochemical actuation, (ii) by actuation based on pH changes. Concepts are proved by delivering a fluorescent dye into neutral and acidic solutions. Drug delivery is confirmed by UV-Visible spectroscopy and Fluorescence microscopy. Finally, Micro/nanostructures with Tangerine, Hollow globular (Pani Poori), Chip, Flake, Rose, Worm, Horn and Celia shapes are synthesized electrochemically and scanning electron microscopic studies are presented. Controlled growth of microstructures on lithographically patterned gold interdigital electrodes is demonstrated with a future goal of creating addressable microstructures. The studies reported in the thesis provide an insight on various applications of PPy microstructures (supercapacitors, sensors and drug delivery systems) developed by a unique methodology based on electrochemically generated gas bubble templates.

Le travail présenté dans cette thèse porte sur l'étude du dimensionnement d'une chaine de conversion électrique en entrainement direct d'un système direct de récupération de l'énergie des vagues (searev). Cette chaine de conversion est composée d'une génératrice synchrone à aimants permanents solidaire d'un volant pendulaire, d'un convertisseur électronique composé de deux ponts triphasés à modulation de largeur d'impulsion, l'un contrôlant la génératrice, l'autre permettant d'injecter l'énergie électrique au réseau. En complément, un système de stockage de l'énergie (batterie de supercondensateurs) est destiné au lissage de la puissance produite. Le dimensionnement de tous ces éléments constitutifs nécessite une approche d'optimisation sur cycle, dans un contexte de fort couplage multi-physique notamment entre les parties hydrodynamique et électromécanique. Dans un premier temps, l'ensemble génératrice-convertisseur, dont le rôle est d'amortir le mouvement d'un volant pendulaire interne, est optimisé en vue de minimiser le coût de production de l'énergie (coût du kWh sur la durée d'usage). Cette optimisation sur cycle est réalisée en couplage fort avec le système houlogénérateur grâce à la prise en compte conjointe de variables d'optimisation relatives à l'ensemble convertisseur-machine mais aussi à la loi d'amortissement du volant pendulaire. L'intégration d'une stratégie de défluxage, intéressante pour assurer un fonctionnement en écrêtage de la puissance, permet, dès l'étape de dimensionnement, de traiter l'interaction convertisseur-machine. Dans un second temps, la capacité énergétique du système de stockage de l'énergie fait l'objet d'une optimisation en vue de la minimisation de son coût économique sur cycle de vie. Pour ce faire, nous définissons des critères de qualité de l'énergie injectée au réseau, dont un lié au flicker, et nous comparons des stratégies de gestion de l'état de charge tout en tenant compte du vieillissement en cyclage des supercondensateurs dû à la tension et à leur température. Dans un troisième temps, à partir de données d'états de mer sur une année entière, nous proposons des dimensionnements de chaines de conversion électrique qui présentent les meilleurs compromis en termes d'énergie totale récupérée et de coût d'investissement. / The work presented in this thesis sets forth the study of the sizing of a direct-drive electrical conversion chain for a direct wave energy converter (SEAREV). This electrical chain is made up of a permanent magnet synchronous generator attached to a pendular wheel and a power-electronic converter made up of two three-phase pulse width modulation bridge, one controlling the generator, the other allowing injecting electrical energy into the grid. In addition, an energy storage system (bank of supercapacitors) is intended to smooth the power output. The sizing of all these components needs an operating cycle optimization approach, in a system context with strong multi-physics coupling, more particularly between hydrodynamical and electromechanical parts. At first, the generator-converter set, whose role is to damp the pendular movement of an internal wheel, is optimized with a view to minimize the cost of energy (kWh production cost). This optimization, based on torque-speed operating profiles, is carried out considering a strong coupling with the wave energy converter thanks to the consideration as design variables, some relatives to the generator-converter sizing but also some relatives to the damping law of the pendular wheel. In addition, the consideration of a flux-weakening strategy, interesting to ensure a constant power operation (levelling), allows, as soon as the sizing step, to deal with the generator-converter interaction. In a second step, the rated energy capacity of the energy storage system is being optimized with a view of the minimization of its economical life-cycle cost. To do this, we define quality criteria of the power output, including one related to the flicker, and we compare three energy managment rules while taking into account the power cycling aging of the supercapacitors due to the voltage and their temperature. In a third step, from yearly sea-states data, we provide sizings of the direct-drive electrical conversion chain that are the best trades-offs in terms of total electrical produced energy and economical investment cost.

The great popularity of portable, wearable, and implantable smart electronics has intensively boosted the development of flexible miniaturized power supplies. Owing to the fast charge/discharge capability, high power delivery, long cycling lifetime, easy fabrication and integration, flexible in-plane micro-supercapacitors (FPMSCs) are of significance as the micropower sources for the next-generation flexible on-chip electronics. In this review, we provide a comprehensive overview about FPMSCs and discuss the recent advances in their fabrication and applications. Particular emphasis is put on the emergent device fabrication technologies of FPMSCs, including deposition techniques, coating strategies, etching methods, and printing technologies. Moreover, we highlight the unique applications of FPMSCs in constructing smart responses and self-powered integrated systems in terms of multifunctional operation modes. Finally, the remaining challenges regarding flexibility, performance improvement, smart response, and microdevice integration of FPMSCs are discussed, which will stimulate further research in this thriving field.

In-plane micro-supercapacitors (MSCs), as promising power candidates for micro-devices, typically exhibit high power densities, large charge/discharge rates, and long cycling lifetimes. The high areal/volumetric capacitances, high energy/power densities, high rate capability, as well as flexibility are the main scientific pursue in recent years. Among diverse electrode materials for MSCs, coordination polymer frameworks are emerging due to the designable porous structure and tunable functionality. However, the unsatisfied electrochemical performance still hinders their practical applications. In this work, we demonstrate the first time an efficient in-situ growth approach to precisely modify the vacancy of Prussian-blue nano-thin films with pyridine by coordination reaction for high energy-density MSCs. Confirmed by the experimental results and density functional theory calculation, the vacancy modification within Prussian-blue network improved the film-forming property, hydrophilicity, and electrochemical activity of the thin films. The resultant MSCs based on pyridine-modified Prussian-blue exhibited an ultrahigh energy density of up to 12.1 mWh cm⁻³ and an ultra-low time constant (t₀) of 0.038 ms, which are the best values among the state-of-the-art in-plane MSCs. This work provides an attractive solution for structural engineering of promising active materials on molecule level toward high-performance micro-energy devices.

Объектом исследования являются электроды на основе нанотубулярного диоксида титана, модифицированные различными способами (термическая обработка, создание композитов с углеродными нанотрубками и частицами металлического никеля). Синтезированные образцы исследовались методом растровой электронной микроскопии и различными электрохимическими методами анализа (гальваностатический заряд-разряд, циклическая вольтамперометрия, импедансная спектроскопия). В результате исследования получены электроды: 1) Т/TiO2-НТ; 2) УНТ/TiO2-НТ; 3) Ni/TiO2-НТ представляющие собой: 1) массивы TiO2-НТ толщиной 3,5 мкм, с внутренним диаметром 70-80 нм и толщиной стенок 30-40 нм; 2) массивы TiO2-НТ с углеродными нанотрубками диаметром 10-30 нм и длиной от десятков нм до десятков мкм на поверхности оксидного слоя; 3) массивы TiO2-НТ, декорированные сферическими наночастицами Ni диаметром 70-100 нм с образованием локальных конгломератов частиц до 500 нм. Результаты работы позволили получить информацию об электрохимических характеристиках синтезированных электродов и преимуществах модификации структур TiO2-НТ для использования их в качестве электродов ионистров. / The object of this research is electrodes based on nanotubular titanium dioxide, modified by various methods (thermal treatment, synthesis of composites with carbon nanotubes and metallic nickel particles). The synthesized samples were investigated by scanning electron microscopy and various electrochemical analysis methods (galvanostatic charge-discharge, cyclic voltammetry, impedance spectroscopy). As a result of the study, were obtained: 1) T/TiO2-NT; 2) CNT/TiO2-NT; 3) Ni/TiO2-NT electrodes, which are: 1) arrays of TiO2-NT 3.5 μm thick, with an inner diameter of 70-80 nm and wall thickness 30-40 nm; 2) arrays of TiO2-NT with carbon nanotubes with a diameter of 10-30 nm and a length from tens of nm to tens of microns on the surface of the oxide layer; 3) arrays of TiO2-NT, decorated with spherical Ni nanoparticles with a diameter of 70-100 nm with the formation of local conglomerates of particles up to 500 nm. The results of the work made it possible to obtain information on the electrochemical characteristics of the synthesized electrodes and the advantages of modifying the TiO2-NT structures to use them as supercapacitor electrodes.

Die vorliegende Arbeit konzentriert sich auf die Synthese von neuartigen hohlen MoSx-Nanomaterialien mit kontrollierbarer Größe und Form durch die kolloidale Template Methode. Ihre möglichen Anwendungen in wässrigen Energiespeichersystemen, einschließlich Superkondensatoren und Li-Ionen-Batterien (LIBs), wurden untersucht. Im ersten Teil wurde eine neue Nanostruktur aus hohlen Kohlenstoff-MoS2-Kohlenstoff-nanoplättchen erfolgreich durch eine L-Cystein unterstützte hydrothermale Methode unter Verwendung von Gibbsit als Templat und Polydopamin (PDA) als Kohlenstoffvorläufer synthetisiert. Nach dem Kalzinieren und Ätzen des Gibbsit Templates wurden gleichförmige Hohlplättchen erhalten, die aus einer sandwichartigen Anordnung von teilweise graphitischem Kohlenstoff und zweidimensional geschichteten MoS2 Flocken bestehen. Die Plättchen haben eine ausgezeichnete Dispergierbarkeit und Stabilität in Wasser sowie eine gute elektrische Leitfähigkeit aufgrund des durch die Kalzinierung von Polydopaminbeschichtungen erzeugten Kohlenstoffs gezeigt. Das Material wird dann in einem symmetrischen Superkondensator mit 1 M Li2SO4 als Elektrolyt aufgebracht, der eine spezifische Kapazität von 248 F/g (0.12 F/cm2) bei einer konstanten Stromdichte von 0.1 A/g und eine ausgezeichnete elektrochemische Stabilität über 3000 Zyklen aufweist, was darauf hindeutet, dass hohle Kohlenstoff-MoS2-Kohlenstoffnanoplättchen vielversprechende Materialien als Kandidaten für Superkondensatoren sind. Im zweiten Teil wurde 21 molare LiTFSI, das sogenannte "Wasser-in-Salz" (WIS) Elektrolyt, in Superkondensatoren mit hohlen Kohlenstoffnanoplättchen als Elektrodenmaterial untersucht. Im Vergleich zu dem im ersten Teil verwendeten 1 molaren Li2SO4-Elektrolyten wurden bei dem vorliegenden WIS Elektrolyt signifikante Verbesserungen in einem breiteren und stabilen Potentialfenster festgestellt, das durch die geringere Leitfähigkeit mit dem Gegenstück leicht beeinflusst wird. Die elektrochemische Impedanzspektroskopie (EIS) wurde ausgiebig eingesetzt, um einen Einblick in die Reaktionsmechanismen der WIS-Superkondensatoren zu erhalten. Zusätzlich wurde auch der Einfluss der Temperatur auf die elektrochemische Leistung im Temperaturbereich zwischen 15 und 55 °C untersucht, was eine hervorragende spezifische Kapazität von 128 F/g bei dem optimierten Zustand von 55 °C ergab. Die EIS-Messungen deckten die Abnahme der angepassten Widerstände mit der Temperaturerhöhung und umgekehrt auf und beleuchteten direkt die Beziehung zwischen elektrochemischer Leistung und Arbeitstemperatur von Superkondensatoren für zuverlässige praktische Anwendungen. Im dritten Teil wurde MoS3, ein amorphes, kettenförmig strukturiertes Übergangsmetall Trichalcogenid, als vielversprechende Anode in "Wasser-in-Salz" Li-Ionen-Batterien (WIS-LIBs) nachgewiesen. Die in diesem Teil verwendeten hohlen MoS3-Nanosphären wurden mittels einer skalierbaren Säurefällungsmethode bei Raumtemperatur synthetisiert, wobei sphärische Polyelektrolytbürsten (SPB) als Schablonen verwendet wurden. Beim Einsatz in WIS-LIBs mit LiMn2O4 als Kathodenmaterial erreicht das präparierte MoS3 eine hohe spezifische Kapazität von 127 mAh/g bei einer Stromdichte von 0.1 A/g und eine gute Stabilität über 1000 Zyklen sowohl in Knopf- als auch in Pouch-Zellen. Der Arbeitsmechanismus von MoS3 in WIS-LIBs wurde auch durch Ex-situ-Röntgenbeugungsmessungen (XRD) untersucht. Während des Betriebs wird MoS3 während der anfänglichen Li-Ionen-Aufnahme irreversibel in Li2MoO4 umgewandelt und dann allmählich in eine stabilere und reversible LixMoOy-Phase (2≤y≤4)) entlang der Zyklen umgewandelt. Amorphes Li-defizientes Lix-mMoOy/MoOz wird bei der Delithiierung gebildet. Die Ergebnisse der vorliegenden Studie zeigen einfache Ansätze zur Synthese hohler MoSx-Nanomaterialien mit kontrollierbarer Morphologie unter Verwendung einer Template-basierten Methode, die auf die vielversprechende Leistung von MoSx für wässrige Energiespeicheranwendungen zurückzuführen sind. Die elektrochemischen Untersuchungen von hohlen MoSx-Nanomaterialien in wässrigen Elektrolyten geben Einblick in die Reaktionsmechanismen von wässrigen Energiespeichersystemen und treiben die Entwicklung von Metallsulfiden für wässrige Energiespeicheranwendungen voran. / The present thesis focuses on the synthesis of novel hollow MoSx nanomaterials with controllable size and shape through the colloidal template method. Their possible applications in aqueous energy storage systems, including supercapacitors and Li-ion batteries (LIBs), have been studied. In the first part, hollow carbon-MoS2-carbon nanoplates have been successfully synthesized through an L-cysteine-assisted hydrothermal method by using gibbsite as the template and polydopamine (PDA) as the carbon precursor. After calcination and etching of the gibbsite template, uniform hollow platelets, which are made of a sandwich-like assembly of partial graphitic carbon and two-dimensional layered MoS2 flakes, have been obtained. The platelets have shown excellent dispersibility and stability in water, and good electrical conductivity due to carbon coating generated by the calcination of polydopamine. The material is then applied in a symmetric supercapacitor using 1 M Li2SO4 as the electrolyte, which exhibits a specific capacitance of 248 F/g (0.12 F/cm2) at a constant current density of 0.1 A/g and an excellent electrochemical stability over 3000 cycles, suggesting that hollow carbon-MoS2-carbon nanoplates are promising candidate materials for supercapacitors. In the second part, 21 m LiTFSI, so-called “water-in-salt” (WIS) electrolyte, has been studied in supercapacitors with hollow carbon nanoplates as electrode materials. In comparison with 1 M Li2SO4 electrolyte used in the first part, significant improvements on a broader and stable potential window have been revealed in the present WISE, which is slightly influenced by the lower conductivity with the counterpart. The electrochemical impedance spectroscopy (EIS) has been extensively employed to provide an insight look on the formation of solid electrolyte interphase in the WIS-supercapacitors. Additionally, the effect of temperature on the electrochemical performance has also been investigated in the temperature range between 15 and 55 °C, yielding eminent specific capacitance of 128 F/g at the optimized condition of 55 °C. The EIS measurements disclosed the decrease of fitted resistances with the increase of temperature and vise versa, directly illuminating the relationship between electrochemical output and working temperature of supercapacitors for reliable practical applications. In the third part, MoS3, an amorphous chain-like structured transitional metal trichalcogenide, has been demonstrated as a promising anode in the “water-in-salt” Li-ion batteries (WIS-LIBs). Hollow MoS3 nanospheres used in this part have been synthesized via a scalable room-temperature acid precipitation method using spherical polyelectrolyte brushes (SPB) as the template. When applied in WIS-LIBs with LiMn2O4 as the cathode material, the prepared MoS3 achieves a high specific capacity of 127 mAh/g at the current density of 0.1 A/g and good stability over 1000 cycles in both coin cells and pouch cells. The working mechanism of MoS3 in WIS-LIBs has also been studied by ex-situ X-ray diffraction (XRD) measurements. During operation, MoS3 undergoes irreversible conversion to Li2MoO4 during the initial Li ion uptake, and is then gradually converted to a more stable and reversible LixMoOy (2≤y≤4)) phase along cycling. Amorphous Li-deficient Lix-mMoOy/MoOz is formed upon delithiation. The results in the present thesis demonstrate facile approaches for synthesizing hollow MoSx nanomaterials with controllable morphologies using a template-based method, which attribute to the promising performance of MoSx for aqueous energy storage applications. The electrochemical studies of hollow MoSx nanomaterials in aqueous electrolytes provide insight into the reaction mechanisms of aqueous energy storage systems and push forward the development of metal sulfides for aqueous energy storage applications.

Laser sind seit ihrer Erfindung im Jahr 1960 essenziell für die Materialbearbeitung und bieten Präzision, Effizienz und Nachhaltigkeit. Während sie anfangs hauptsächlich für die Makrobearbeitung eingesetzt wurden, haben Fortschritte bei kurzwelligen und ultrakurz gepulsten Lasern die präzise Mikro- und Nanobearbeitung ermöglicht, was dem wachsenden Bedarf an umweltfreundlicher Fertigung entspricht. Diese Arbeit konzentriert sich auf zwei laserbasierte Techniken für die nachhaltige Elektrodenproduktion: Laser-induced forward transfer (LIFT) und Laserkohlenstoffisierung. Kapitel 1 führt diese Methoden ein. Kapitel 2 untersucht LIFT für den Polymertransfer, wobei die Oberflächenhaftung und Benetzungseigenschaften untersucht werden, um definierte Polymermikrostrukturen zu erzeugen. Die Studie bietet Einblicke in die Optimierung polymerbasierter Geräte und stellt die LIFT-unterstützte Synthese von Metalloxidmustern für Elektrodenstrukturen und Heteroübergänge vor. Kapitel 3 befasst sich mit der Laserkohlenstoffisierung unter Verwendung von sodium lignosulfonate (SLS), einem Nebenprodukt der Papierindustrie, als nachhaltigem Kohlenstoffvorläufer. Durch die Integration einer haftenden Polymerschicht werden robuste, laser patterned carbon (LP-C) in einem einzigen Schritt hergestellt. Diese LP-C-Elektroden, deren Eigenschaften anpassbar sind, zeigen eine hervorragende Leistung in Superkondensatoren und Dopaminsensoren und weisen eine hohe Kapazität, Energiedichte und Stabilität auf. Diese Arbeit hebt das Potenzial von SLS-basierten LP-C-Elektroden für nachhaltige Energiespeicherung und Biosensorik hervor und trägt zur Weiterentwicklung umweltfreundlicher elektrochemischer Systeme bei. / Lasers have been essential in materials processing since their invention in 1960, offering precision, efficiency, and sustainability. While initially used for macro processing, advances in short-wavelength and short-pulse lasers have enabled precise micro- and nano-scale processing, aligning with the growing demand for eco-friendly manufacturing. This thesis focuses on two laser-based techniques for sustainable electrode production: Laser Induced Forward Transfer (LIFT) and laser carbonization. Chapter 1 introduces these methods. Chapter 2 explores LIFT for polymer transfer, investigating surface adhesion and wetting properties to create defined polymer microstructures. The study provides insights into optimizing polymer-based devices and presents LIFT-assisted metal oxide synthesis for patterned electrode structures and heterojunctions. Chapter 3 examines laser carbonization using sodium lignosulfonate (SLS), a paper industry byproduct, as a sustainable carbon precursor. By integrating an adhesive polymer layer, robust laser-patterned carbon (LP-C) electrodes are fabricated in a single step. These LP-C electrodes, with tunable properties, show excellent performance in supercapacitors and dopamine biosensors, demonstrating high capacitance, energy density, and stability. This work highlights the potential of SLS-based LP-C electrodes for sustainable energy storage and biosensing applications, advancing eco-friendly electrochemical systems.