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La hibridación de minerales arcillosos con polímeros conductores recibe gran interés por diferentes aplicaciones potenciales, incluida la remediación ambiental. Esta tesis contiene tres partes del estudio, en primer lugar, estudia y compara las propiedades electroquímicas de dos arcillas diferentes, montmorillonita (Mont) y diatomita (Diat), y sus respectivos materiales híbridos arcilla/PEDOT-PSS en medio H2SO4. Los materiales híbridos se prepararon por electropolimerización de EDOT en presencia de PSS. Se analizaron las propiedades físico-químicas y electroquímicas de ambas arcillas mediante diferentes técnicas, y se investigó la influencia de las propiedades de la arcilla en la electropolimerización y la electroactividad de los híbridos arcilla/PEDOT-PSS resultantes. En concreto, la sonda redox Fe2+/Fe3+ y la oxidación de diclofenaco, como contaminante emergente farmacéutico modelo, se utilizaron para probar la capacidad de transferencia de electrones y la respuesta oxidativa, respectivamente, de los híbridos arcilla/PEDOT-PSS. Los resultados demuestran que, a pesar de su baja conductividad eléctrica, el Mont es un material electroactivo en sí mismo con una buena capacidad de transferencia de electrones. Por el contrario, el Diat no muestra electroactividad. La hibridación con PEDOT generalmente mejora la electroactividad de las arcillas, pero las propiedades de la arcilla afectan la eficiencia de electropolimerización y la electroactividad de los híbridos, por lo que Mont/PEDOT muestra propiedades electroquímicas mejoradas. Se demuestra que los híbridos de arcilla/PEDOT-PSS exhiben capacidad de oxidación de diclofenaco y sensibilidad a la concentración de diclofenaco. Se sintetizaron diferentes materiales híbridos a base de arcilla en un solo paso mediante polimerización química de EDOT en presencia de la arcilla sin o con nanofibras de carbono (CNF). Estos materiales fueron caracterizados con diferentes técnicas y estudiados por su potencial aplicación en la remoción de diclofenac y Radium, contaminantes emergentes modelo, del agua. Para ello se analizó la termodinámica y cinética de adsorción de diclofenaco y radio sobre los diferentes materiales. En el caso del Diclofenaco, los resultados obtenidos indican que el método de síntesis propuesto permite producir fácilmente los materiales híbridos con rendimientos del 80 - 90 %. La caracterización de estos materiales muestra que la estructura mesoporosa y alta área superficial (ca. 250 m2/g) de la arcilla no se ve afectada de forma notable por su combinación con PEDOT y/o los CNFs. La termogravimetría indica que se han obtenido materiales híbridos con alrededor del 10 % en peso de PEDOT sin y con 4 y 8 % en peso de CNF. La combinación de SEM con XPS y FTIR señala que PEDOT se ha cultivado con éxito alrededor de partículas de arcilla. La comparación de las isotermas de adsorción de diclofenaco indica que la hibridación con PEDOT mejora en gran medida la capacidad de adsorción de la arcilla. La adsorción de la isoterma resultante muestra la adsorción más alta con CNF y Clay/PEDOT con 340 mg/g y 220 mg/g respectivamente. Los datos de equilibrio se aplicaron a dos modelos de isoterma, y los resultados obtenidos sugirieron que la adsorción se siguió mejor con el modelo de Langmuir para Clay/PEDOT y Clay, con una capacidad máxima de adsorción de monocapa de 227,01 mg/g y 20,44 mg/g respectivamente. Por el contrario, fueron mejor ajustados por el modelo de Freundlich para el resto de los materiales, indicando adsorción heterogénea y la posibilidad de formación de multicapas en estos casos. Los datos cinéticos obtenidos para la adsorción se ajustaron mejor a una ecuación de velocidad de pseudo segundo orden para todos los materiales, con una capacidad máxima de adsorción en equilibrio de 18,24 mg/g para Clay/PEDOT. Este hallazgo sugiere que la adsorción se estaba produciendo a través del mecanismo químico. En el caso del Radio, se sintetizaron diferentes materiales híbridos a base de arcilla en un solo paso mediante polimerización química de EDOT y anilina en presencia de arcilla sin o con nanofibras de carbono (CNF). Estos materiales fueron caracterizados con diferentes técnicas y estudiados por su potencial aplicación en la remoción de radio del agua. Para este propósito, se utilizó una muestra de salmuera, recolectada de la salida de la mina subterránea, para probar la remoción de radio. El estudio que se realizó y se detalla en el documento muestra una gran eficacia en la eliminación de radio de las muestras de agua. La característica de los materiales se realizó mediante XRD, TG, FE-SEM, fluorescencia de rayos X y análisis de adsorción-desorción de N2. Los experimentos demostraron que arcilla/PEDOT, arcilla/PEDOT/10 % CNF y arcilla/PANI tienen una eficiencia de eliminación de radio significativamente menor. El uso de arcilla y arcilla que ha sido alterada químicamente por polímeros y nanofibras de carbono es una forma potencial de eliminar el radio del agua. El uso de un material híbrido a base de arcilla es una opción potencial para eliminar el radio del agua. El estudio realizado y detallado en el documento examinó una variedad de nanofibras de carbono y polímeros a base de arcilla (PEDOT, PANI), ya que algunos de ellos muestran una gran eficacia para eliminar el radio de las muestras de agua. La característica de los materiales se realizó mediante XRD, TG, FE-SEM, fluorescencia de rayos X y análisis de adsorción-desorción de N2. Para las pruebas de remoción de radio, se utilizó una muestra de salmuera, recolectada de la salida de una mina subterránea. Los experimentos demostraron que arcilla/PEDOT, arcilla/PEDOT/10 % CNF y arcilla/PANI tienen una eficiencia de eliminación de radio significativamente menor.

This thesis presents work done to improve the switching speed and contrast performance of electrochromic devices. Layer-by-Layer (LbL) assembly was used to deposit thin electrochromic films of materials ranging from organic, inorganic, conducting polymers, etc. The focus was on developing new materials with high contrast and long lifecycles. A detailed switching-speed study of solid-state EC devices of already-developed (PEDOT (Poly(3,4-ethylenedioxythiophene)), polyviologen, inorganic) materials and some new materials (Prodot-Sultone) was performed. Work was done to achieve the optimum thickness and number of bilayers in LbL films resulting in high-contrast and fast switching. Device sizes were varied for comparison of the performance of the lab-made prototype device with the commercially available "small pixel" size displays. Symmetrical EC devices were fabricated and tested whenever conducting polymers are used as an EC material. This symmetrical configuration utilizes conducting polymers as an electroactive layer on each of two ITO-coated substrates; potential is applied to the two layers of similar conducting polymers and the device changes color from one redox state to another. This method, along with LbL film assembly, are the main factors in the improvement of switching speed results over already-published work in the literature. PEDOT results show that EC devices fabricated by LbL assembly with a switching speed of less than 30 ms make EC flat-panel displays possible by adjusting film thickness, device size, and type of material. The high contrast value (84%) for RuP suggests that its LbL films can be used for low-power consumption displays where contrast, not fastest switching, is the prime importance. In addition to the electrochromic work, this thesis also includes a section on the application of LbL assembly in fabricating electromechanical bending actuators. For bending actuators based on ionic polymer metal composites (IPMCs), a new class of conductive composite network (CNC) electrode was investigated, based on LbL self-assembled multilayers of conductive gold (Au) nanoparticles. The CNC of an electromechanical actuator fabricated with 100 bilayers of polyallylamine hydrochloride (PAH)/Au NPs exhibits high strain value of 6.8% with an actuation speed of 0.18 seconds for a 26 µm thick IPMC with 0.4 µm thick LbL CNCs under 4 volts. / Ph. D.

Cette thèse propose tout d’abord une méthode originale, appelée 2 en 1, de construction contrôlée, couche-par-couche, de films de polyélectrolytes, basée sur le dépôt d’un unique complexe polycation-polyanion. Détaillée dans le cas du poly(éthylènedioxythiophène)-poly(styrènesulfonate) PEDOT-PSS, la méthode est ensuite étendue avec le même succès à d’autres complexes (poly(éthylèneimine) branché-poly(4 styrènesulfonate), poly(diallyldiméthylammonium)-poly(4 styrènesulfonate) et poly(allylamonium)-poly(4 styrènesulfonate)).Les films 2 en 1 de PEDOT PSS sont robustes vis-à-vis d’un recuit thermique et possèdent une conductivité électronique indépendante de leur épaisseur. Cette conductivité peut être améliorée en utilisant un composite contenant des nanoparticules d’or Au Np PEDOT PSS. Des superstructures alternant dépôts de PEDOT PSS et de composite ont, en outre, pu être construites.La construction est contrôlée non seulement sur des substrats rigides (verre, wafer de silicium) mais également sur des substrats élastomère de type silicone (polydiméthylsiloxane PDMS). Le traitement du PDMS par polymérisation plasma d’EDOT sous vide permet le dépôt subséquent de films 2 en 1 de PEDOT PSS. Par ailleurs, la pulvérisation cathodique d’or sur le PDMS permet d’obtenir des conducteurs étirables, de surcroît utilisables comme substrats de films 2 en 1 de PEDOT PSS.Enfin, de nouveaux complexes aqueux synthétisés par voie chimique à partir d’EDOT et d’un polysaccharide (sulfate de chondroïtine A) ont conduit à des films présentant une très bonne conduction qui peut être augmentée par inclusion de nanoparticules d’or. Ces nouveaux composés sont porteurs d’un potentiel très prometteur. / This thesis proposes firstly an original method, called 2 in 1 method, for controlled, layer-by-layer, polyelectrolytes film buildup, based on the deposition of a sole polycation-polyanion complex. Detailed on the case of poly(ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS), the method was then extended with the same success to other complexes (branched poly(ethyleneimine)-poly(4 styrenesulfonate), poly(diallyldimethylammonium)-poly(4 styrenesulfonate) and poly(allylamonium)-poly(4 styrenesulfonate)).The 2 in 1 PEDOT PSS films are robust regarding thermal annealing and have an electronic conductivity independent of their thickness. This conductivity can be improved by using a composite containing gold nanoparticles Au Np PEDOT PSS. Superstructures alternating PEDOT PSS and composite depositions were also obtained.Film buildup is controlled not only on rigid substrates (glass, silicon wafer) but also on elastomeric substrates of the silicon type (polydimethylsiloxane PDMS). The treatment of PDMS by vacuum plasma enhanced chemical vapor deposition (PECVD) of EDOT allows subsequent deposition of 2 in 1 PEDOT-PSS films. Besides, gold sputter deposition on PDMS reaches stretchable conductors. Gold sputtered PDMS can further act as a substrate for 2 in 1 PEDOT-PSS films.Finally, new aqueous complexes, chemically synthesized from EDOT and a polysaccharide (chondroitin sulfate A), lead to films which exhibit a very good conduction, which can be improved by the inclusion of gold nanoparticles. These new complexes are very promising in the field of conductive biomaterials.

Dans l'objectif d'améliorer la mise en forme des polymères semi-conducteurs tels que le poly (3,4-éthylènedioxythiophène) et la polyaniline, nous avons développé leur synthèse par polymérisation en dispersion de leurs monomères respectifs en utilisant le poly(oxyde d'éthylène), le poly (vinyl alcool), le poly [(N-vinylpyrrolidone)-co-(vinyl alcool)] et le poly [(N-vinylpyrrolidone)-b-(vinyl alcool)] comme stabilisants réactifs dans des milieux dispersants aqueux. Des nano-objets de nature et de structure bien définis ont été obtenus. Afin de moduler la conductivité et les propriétés opto-électroniques de ces nano-objets, leurs composites avec des métaux tels que l'or, l'argent et le cuivre ont été préparés en utilisant les sels métalliques correspondants comme co-oxydants au cours de la polymérisation en dispersion. La morphologie des nano-objets a notamment été évaluée par Microscopie Electronique en Transmission, Microscopie Electronique à Balayage, et Microscopie à Force Atomique. Le nature cœur-écorce de ces nano-objets, le niveau de dopage et la présence de métaux dans les nano-composites ont été examinés par spectrométrie de photoélectrons induits par rayons X. / With the objective to improve the processability of “stiff” semi-conducting polymers, well defined poly(3,4-ethylenedioxythiophene) and polyaniline core-shell nano-objects were synthesized by dispersion polymerization of their respective monomers using poly(ethylene oxide), poly(vinyl alcohol), poly[(N-vinylpyrrolidone)-co-(vinyl alcohol)] and poly[(N-vinylpyrrolidone)-b-(vinyl alcohol)]-based reactive stabilizers in aqueous dispersant media. In order to improve the conductivity and opto-electronic properties of these nano-objects, their composite with gold, silver and copper were prepared using the metal salts as co-oxidants during dispersion polymerization. The morphology of the nano-objects was observed by microscopy analyses such as Transmission Electron Microscopy, Scanning Electron Microscopy, and Atomic Force Microscopy. The core-shell nature of these nano-objects, doping level and the presence of metals in the nano-composites were examined by X-rays Photoelectron Spectroscopy.

Trilayer polypyrrole microactuators that can operate in air have previously been developed. They consist of two outer layers ofthe electroactive polymer polypyrrole (PPy) and one inner layer of a porous poly(vinylidene flouride) (PVDF) membranecontaining a liquid electrolyte. The two outer layers of PPy are each connected with gold electrodes and separated by the porousPVDF membrane. This microtool is fabricated by bottom-up microfabrication However, porous PVDF layer is not compatible with bottom upmicrofabrication and highly swollen SPE suffers from gold electrode delamination. Hence, in this MSc project/thesis a novelmethod of flexible electrode fabrication with conducting polymers was developed by soft lithography and drop-on-demandprinting. The gold electrodes were replaced by patterned vapor phase polymerized (VPP) poly(3,4-ethylenedioxythiophene) (PEDOT)electrodes due to its high electrical conductivity and versatile process ability. The replacement of the stiff gold electrodes byflexible and stretchable PEDOT allowed high volume change of the material and motions. The PEDOT electrodes werefabricated by patterning the oxidant iron tosylate using microcontact printing and drop-on-demand printing. Moreover, thePVDF membrane has been replaced by a nitrile butadiene rubber/poly(ethylene oxide) semi-interpenetrating polymer network(IPN) to increase ion conductivity and strechability and hence actuator performance.

Electroactive textile fibers are key components in smart and interactive textile applications. In previous research on textile base conductive fibers, viscose fibers were coated with poly (3,4-ethylenedioxythiophne) (PEDOT) using oxidative chemical vapor deposition (oCVD) technique[1]. Ferric chloride was used as oxidant and reaction conditions were optimized at which better electrical as well as mechanical properties of conductive viscose fibers could be achieved. In this thesis work, effect of new parameters such as pretreatment of viscose fibers with solvents, drying of oxidant treated viscose fibers at different time and temperature and comparison of two different oxidants have been tried. One new and important oxidant, ferric (III) p-toluene sulfonate or ferric (III) tosylate, used to prepare PEDOT coated viscose fibers and then compared with PEDOT coated viscose fibers prepared using oxidant ferric (III) chloride. Viscose fibers have been treated with two well know solvents, acetone and ethyl acetate before soaking in oxidant solution. Oxidant enriched fibers dried at different temperature for variable time prior to polymerization step. Knitted structures of conductive viscose fibers have been prepared. Hand washing of PEDOT coated viscose fibers with tap water and machine washing of knitted structures according to the international standard ISO EN-6330 have been performed and washing effects were investigated. Effects of all of the above mentioned variables on electromechanical properties of PEDOT coated viscose fibers were studied by using tensile testing, TGA analysis, FTIR spectra and conductivity measurements. Stretch sensing properties of knitted structures; before and after washing, were determined on cyclic tester. The purpose of this study is to enhance the properties of PEDOT-coated viscose fibers by controlling different parameters and to evaluate their usage as stretch sensors as well as to check the washability of PEDOT coated viscose fibers and knitted structures. Better electromechanical properties were achieved on new parameters and PEDOT coated viscose fibers were successfully utilized as stretch sensors. PEDOT coated viscose fibers could have potential to apply in areas such as, military textiles, medical textiles and sensors. / Program: Master programme in Textile Technology

Following the discovery of electronic conductivity in doped polyacetylene, various studies on conducting polymers have been investigated. These polymers are essentially characterized by the presence of conjugated bonding on polymer backbone, which facilitates formation of polarons and bipolarons as charge carriers. Poly(3,4-ethylenedioxythiophene) (PEDOT) is an interesting polymer because of high electronic conductivity, ease of synthesis and high chemical stability. Electrochemically prepared PEDOT is more interesting than the polymer prepared by chemical routes because it adheres to the electrodes surface and the PEDOT coated electrodes can directly be used for various applications such as batteries, supercapacitor, sensors, etc. A majority of the studies described in the thesis are based on PEDOT. Studies on polyanthanilic acid and reduction of hydrogen peroxide on stainless steel substrate are also included. Chapter 1 provides an introduction to conducting polymers with a focus on synthesis, electrochemical characterization and applications of PEDOT. In Chapter 2, microscopic and impedance spectroscopic characterization of PEDOT coated on stainless steel (SS) and indium tin oxide (ITO) coated glass substrates are described. Electrosynthesis of PEDOT is carried out on SS electrodes by three different techniques, namely, potentiostatic, galvanostatic and potentiodynamic techniques. The SEM images of PEDOT prepared by the galvanostatatic and potentiostatic routes indicate globular morphology. However, it is seen that porosity increases by increasing the current or the potential. In the cases of both galvanostatic and potentiostatic routes, the oxidation of EDOT to form PEDOT takes place continuously during preparation. However, in the case of potentiodynamic experiment between 0 and 0.9 V vs. SCE (saturated calomel electrode), the formation of PEDOT occurs only when the potential is greater than 0.70 V. During multicycle preparation to grow thicker films of PEDOT, formation of PEDOT takes place layer by layer, a layer of PEDOT being formed in each potential cycle. PEDOT prepared in the potential ranges 0-0.90 V and 0-1.0 V show globular morphology similar to the morphology of the galvanostatically and potentiostatically prepared polymer. If prepared in the potential ranges 0-1.1 V and 0-1.2 V, the PEDOT films have rod-like and fibrous morphology. This is attributed to larger amount of PEDOT formed in each cycle in comparison with lower potential ranges and also to partial oxidation of PEDOT at potentials ≥ 1.10 V. PEDOT is also electrochemically prepared on ITO coated glass substrate. Preparation is carried out under potentiostatic conditions in the potential range between 0.9 and 1.2 V. Atomic force microscopy (AFM) studies indicate a globular topography for PEDOT films prepared on ITO coated glass plates. The height and width of globules increase with an increase in deposition potential. The PEDOT coated SS electrodes are subjected to electrochemical impedance spectroscopy studies in 0.1 M H2SO4. The Nyquist plot of impedance consists of a depressed semicircle, which arises due to a parallel combination of the polymer resistance and double-layer capacitance (Cdl). Impedance data are analyzed. Studies on electrooxidation of methanol, formic acid, formaldehyde and ethanol on nanocluster of Pt and Pt-Ru deposited on PEDOT/C electrode are reported in Chapter 3. Studies on electrooxidation of small molecules are important in view of their promising applications in fuel cells. Films of PEDOT are electrochemically deposited on carbon paper. Nanoclusters of Pt and bimetallic Pt-Ru catalysts are potentiostatically deposited on PEDOT/C electrodes. Catalysts are also prepared on bare carbon paper for studying the effect of PEDOT. The presence of PEDOT film on carbon paper allows the formation of uniform, well dispersed nanoclusters of Pt as well as Pt-Ru catalysts. TEM studies suggest that the nanoclusters of about 50 nm consist of nanoparticles of about 5 nm in diameter. Electrooxidation of methanol, formic acid, formaldehyde and ethanol are studied on Pt-PEDOT/C and PtRu-PEDOT/C electrodes by cyclic voltammetry and chronoamperometry. The data for oxidation of these small organic molecules reveal that PEDOT imparts a greater catalytic activity for the Pt and Pt-Ru catalysts. Results of these studies are described in Chapter 3. In Chapter 4, PEDOT is coated on SS substrate to investigate phenol oxidation. Studies on electrochemical oxidation of phenol are interesting because it is important to remove phenol from contaminated water or industrial effluents. Deactivation of the anode due to the formation and adsorption of polyoxyphenylene on its surface is a common problem for a variety of electrode materials, during phenol oxidation. Investigations on suitable anode materials, which can undergo no or moderate poisoning by polyoxyphenylene, are interesting. In the present study, it is shown that the electrooxidation rate of phenol is greater on PEDOT/SS electrodes than on Pt. Deactivation of PEDOT/SS electrode is slower in relation to Pt. The oxidation of phenol on PEDOT/SS electrode occurs to form both polyoxyphenylene and benzoquinone in parallel. Cyclic voltammetry of phenol oxidation is studied by varying the concentration of phenol, sweep rate and thickness of PEDOT. Ac impedance studies indicate a gradual increase in polymer resistance due to adsorption of polyoxyphenylene during multi sweep cyclic voltammetry. This investigation reveals that PEDOT coated on a common metal or alloy such as SS is useful for studying electrooxidation of phenol, which is generally studied on a noble metal based electrodes. Electrochemically prepared PEDOT is used for supercapacitor studies and the results are presented in Chapter 5. Generally, electronically conducting polymers possess high capacitive properties due to pseudo-faradaic reactions. PEDOT/SS electrodes prepared in 0.1 M H2SO4 are found to yield higher specific capacitance (SC) than the electrodes prepared from neutral aqueous electrolyte. The effects of concentration of H2SO4, concentration of SDS, potential of deposition and nature of supporting electrolytes used for capacitor studies on SC of the PEDOT/SS electrodes are studied. Specific capacitance values as high as 250 F g-1 in 1 M oxalic acid are obtained during the initial stages of cycling. However, there is a decrease in SC on repeated charge-discharge cycling. Spectroscopic data reflect structural changes in PEDOT on extended cycling. Self-doped PANI is expected to possess superior electrochemical characteristics in relation to PANI. The self-doping is due to the presence of an acidic group on the polymer chain. However, self-doped PANI is soluble in acidic solutions against insolubility of PANI. In the present study, poly(anthranilic acid), PANA, is encapsulated in porous Nafion membrane by chemical and a novel electrochemical methods. PANA present in solid form in Nafion membrane does not undergo dissolution in acidic solutions. The methods of preparation and various electrochemical, optical and spectroscopic characterizations studies of PANA-Nafion are described in Chapter 6. Electroreduction of H2O2 is studied on sand-blasted stainless steel (SSS) electrode in an aqueous solution of NaClO4 and the details are reported in Chapter 7. The cyclic voltammetric reduction of H2O2 at low concentrations is characterized by a cathodic peak at -0.40 V versus standard calomel electrode (SCE). Cyclic voltammetry is studied by varying the concentration of H2O2 in the range from 0.2 mM to 20 mM and the sweep rate in the range from 2 to 100 mV s-1. Cyclic voltammograms at concentrations of H2O2 higher than 2 mM or at high sweep rates consist of an additional current peak, which may be due to the reduction of adsorbed species formed during the reduction of H2O2. Amperometric determination of H2O2 at -0.50 V vs. SCE provides the detection limit of 5 μM H2O2. A plot of current density versus concentration has two linear segments suggesting a change in the mechanism of H2O2 reduction at concentrations of H2O2 ≥ 2 mM. From the rotating disc electrode study, diffusion co-efficient of H2O2 and rate constant for reduction of H2O2 are evaluated. Thus, stainless steel, which is inexpensive and a common alloy, is useful for studying electrochemical reduction of H2O2 and also for analytical application. This work is initiated to study the reduction of H2O2 on PEDOT/SS electrodes. As a result of preliminary experiments, it is found that PEDOT does not exhibit any influence on the kinetics of H2O2 reduction. Therefore studies conducted using bare stainless steel are included in this chapter. Results of the above studies are described in the thesis.

Detection of chemicals is a vital part of chemistry. For this reason, many detection systems are developed by scientists and every detection system has its own advantages. Raman spectroscopy is one of these detection systems having many advantages. However, this technique suffers from low signal intensity disadvantage. By developing a well prepared substrate, this problem can be easily solved / moreover, even single molecule detection can be possible. In this study, a novel surface enhanced Raman scattering (SERS) substrate was prepared in two steps: In the first step, ethylenedioxythiophene (EDOT) monomer was polymerized electrochemically onto indium tin oxide (ITO) coated glass. In the next step, silver ions were reduced electrochemically onto surface prepared in the previous step.In the substrate preparation part, the reduction potential of silver ion, the concentration of silver ions in solution, the polymer film thickness and reduced silver amount on substrates were optimized to get the best SERS performances from substrates. The prepared substrates were characterized by cyclic voltammetry (CV), ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX) attached to SEM. In the SERS performance investigation part, homogeneity and the shelf life of the prepared silver-PEDOT substrates were tested. Homogeneity is very important in terms for the applications of Raman technique in quantitative analysis since most of the reported substrates are lack homogeneity consideration, our study will be an important contribution to the literature. The stability of the substrate was investigated for a period of one month. The very small change in the signal at the end of one month indicated that the substrate can be used even longer time with high efficiency. In all the studies, brilliant cresyl blue (BCB) is used as a model compound. Some important Raman active chemicals, namely, rhodamine 6G (R6G) and 4-mercapto benzoic acid (4-MBA) were detected by using the prepared substrates.

In this thesis, two recently discovered polymorphs of LiFeSO4F, adopting a tavorite- and triplite-type structure, were investigated as potential candidates for use as cathode materials in Li-ion batteries. The studies aimed at enriching the fundamental understanding of the synthetic preparations, structural properties, and electrochemical functionality of these materials. By in situ synchrotron X-ray diffraction (XRD), the formation mechanism of the tavorite-type LiFeSO4F was followed starting from two different sets of precursors, FeSO4∙H2O + LiF, and Li2SO4 + FeF2. The results indicated that the formation of LiFeSO4F is possible only through the structurally related FeSO4∙H2O, in line with the generally recognized topotactic reaction mechanism. Moreover, an in-house solvothermal preparation of this polymorph was optimized with the combined use of XRD and Mössbauer spectroscopy (MS) to render phase pure and well-ordered samples. Additionally, the triplite-type LiFeSO4F was prepared using a facile high-energy ball milling procedure. The electrochemical performance of as-prepared tavorite LiFeSO4F was found to be severely restricted due to residual traces of the reaction medium (tetraethylene glycol (TEG)) on the surface of the synthesized particles. A significantly enhanced performance could be achieved by removing the TEG residues by thorough washing, and a subsequent application of an electronically conducting surface coating of p-doped PEDOT. The conducting polymer layer assisted the formation of a percolating network for efficient electron transport throughout the electrode, resulting in optimal redox behavior with low polarization and high capacity. In the preparation of cast electrodes suitable for use in commercial cells, reducing the electrode porosity was found to be a key parameter to obtain high-quality electrochemical performance. The triplite-type LiFeSO4F showed similar improvements upon PEDOT coating as the tavorite-type polymorph, but with lower capacity and less stable long-term cycling due to intrinsically sluggish kinetics and unfavorable particle morphology. Finally, the Li+-insertion/extraction process in tavorite LiFeSO4F was investigated. By thorough ex situ characterization of chemically and electrochemically prepared LixFeSO4F compositions (0≤x≤1), the formation of an intermediate phase, Li1/2FeSO4F, was identified for the first time. These findings helped redefine the (de)lithiation mechanism which occurs through two subsequent biphasic reactions, in contrast to a previously established single biphasic process.