This thesis deals with comprehensive study and design of recovery system of a road vehicle powered by human power. It contains an overview of different types of heat recovery devices, their characteristics, advantages, disadvantages and applicability in the construction of such a vehicle.

This dissertation deals with the electrode materials, liquid and gel electrolytes suitable for supercapacitors. In the field of electrode materials were investigated carbon materials based on carbon blacks, expanded and micronized graphite suitable for supercapacitors working on the principle electrochemical double layer. Another area which this thesis deals with are aprotic liquid electrolytes prepared from suitable types of salts and aprotic solvents. The last part is focused on the preparation and subsequent electrochemical characterization of gel polymer electrolytes in order to increase the ionic conductivity of these electrolytes.

This master’s thesis contains basic description od ADAHRS system, DO-160 standard and mainly focuses on power supply desing with supercapacitors backup. It initialy deals with power supply requirements and continues with block diagram and multiple 5 V supply solutions. For selected 5 V supply it describes more deeply its properities and options. As the main theme it deals with providing power supply backup using supercapacitors – selecting particular method and configuring supercapacitor charging/discharging controller. It also includes tolerance and stress analysis of the components used in design. Lastly it describes testing of the final product.

The purpose of this project was the modeling, optimization and prediction of a hybrid system composed of a fuel cell, a dc-dc converter and a supercapacitor in series. Lab tests were performed for each device to understand their behavior, and then each one was modeled using software (Simulink). The validation of the model was done by comparing its results with measured data; finally the model was used for the optimization and the prediction of the hybrid system

In this work, a high-performance hybrid supercapacitor is assembled with N-doped reduced graphene oxide (N-rGO) decorated with Fe2O3 (Fe2O3/N-rGO) as the anode, and NiCo layered double hydroxide integrated with conductive Co(OH)2 (NiCo LDH/Co(OH)2) as the cathode. The two main pseudo-capacitive materials are modified by different materials (N-rGO and Co(OH)2) to enhance the conductivity. For anode, the Fe2O3 nanoparticles are uniformly dispersed on N-rGO via a facile solvent-thermal method. The highly conductive Fe2O3/N-rGO exhibits a superior capacitance of 912.9F/g at 1 A/g and retains 84% at 30 A/g. The NiCo LDH/Co(OH)2 cathode also synthesized by a convenient solvent-thermal method delivers a high specific capacitance of 2220.0F/g at 1 A/g and retains 70% at a high current density of 50 A/g. Utilizing these electrodes, we successfully fabricate a hybrid battery-like supercapacitor with an excellent energy density of 103.3 Wh/kg at an outstanding power density of 790 W/kg, an excellent capacitance of 296.3F/g at 1 A/g and a remarkable cyclic stability with 92% retention after 1000 cycles at 10 A/g. Due to the elaborately designed electrode materials, the battery-like supercapacitor exhibits excellent electrochemical properties and is an inspiration for future energy storage devices.

With a growing demand for electrical energy storage materials, lignin-derived carbon materials have received increasing attention in recent years. As a highly abundant renewable carbon source, lignin can be converted to a variety of advanced carbon materials with tailorable chemical, structural, mechanical and electrochemical properties through thermochemical conversion (e.g. pyrolysis). However, the non-uniformity in lignin structure, composition, inter-unit linkages and reactivity of diverse lignin sources greatly influence lignin fractionation from plant biomass, the pyrolysis chemistry, and property of the resulting carbon materials. To introduce a better use of lignocellulosic biomass to biofuels and co-products, it is necessary to find novel ways to fractionate lignin and cellulose from the feedstock at high efficacy and low cost. Deep eutectic solvent (DES) was used to extract lignin from high lignin-content walnut and peach endocarps. Over 90% sugar yields were achieved during enzymatic hydrolysis of DES pretreated peach and walnut endocarps while lignins were extracted at high yields and purity. The molecular weights of the extracted lignin from DES pretreated endocarp biomass were significantly reduced. The native endocarp lignins were SGH type lignins with dominant G-unit. DES pretreatment decreased the S and H-unit which led to an increase in condensed G-units, which may contribute to a higher thermal stability of the isolated lignin. Lignin slow pyrolysis was investigated using a commercial pyrolysis–GC/MS system for the first time to link pyrolysis chemistry and carbon material properties. The overall product distributions, including volatiles and solid product were tracked at different heating rates (2, 20, 40 ℃/min) and different temperature regions (100-200, 200-300 and 300-600 ℃). Results demonstrate that changes in reaction chemistry as a factor of pyrolysis conditions led to changes in yield and properties of the resulting carbon materials. Physical and chemical properties of the resulting carbon material, such as porosity, chemical composition and surface functional groups were greatly affected by lignin slow pyrolysis temperature and heating rate. Lignin-derived activated carbons (AC) were synthesized from three different lignin sources: poplar, pine derived alkaline lignin and commercial kraft lignin under identical conditions. The poplar lignin-derived ACs exhibited a larger surface area and total mesopore volume than softwood lignin-derived AC, which contribute to a larger electrochemical capacitance over a range of scan rates. The presence of oxygen-containing functional groups in all lignin-derived ACs, which participated in redox reaction and thus contributed to an additional pseudo-capacitance. By delineating the carbonization and activation parameters, results from this study suggest that lignin structure and composition are important factors determining the pore structure and electrochemical properties of the derived carbon materials. A 3-dimensional, interconnected carbon/silicon nanoparticles composite synthesized from kraft lignin (KL) and silicon nanoparticles (Si NPs) is shown to have a high starting specific capacity of 2932 mAh/g and a retaining capacity of 1760 mAh/g after 100 cycles at 0.72 A/g as negative electrode in a half-cell lithium-ion battery (LIB) test. It was found the elemental Si and C of the C/Si NPs were most likely linked via Si-O-C rather than direct Si-C bond, a feature that helps to alleviate the mechanical degradation from Si volume change and assure a sound electronic and ionic conductivity for enhanced electrochemical performance. EGA-MS and HC-GC/MS analyses suggest that the interaction of the Si, O and C can be tailored by controlling pyrolysis conditions. This study systematically investigated the interconnecting aspects among lignin source, pyrolysis chemistry, characteristics of the derived carbon materials and electrochemical performance. Such knowledge on the processing-structure-function relationships serves as a basis for designing lignin-based carbon materials for electrochemical energy storage applications.

Afin de proposer une alternative aux supercondensateurs utilisant des électrolytes aqueux sous forme liquide produits par la société Hutchinson, ces travaux de thèse ont porté sur le développement de gels ioniques, composés de polymères réticulés gonflés par un liquide ionique, pouvant être utilisés comme électrolytes. L’objectif est donc ici de synthétiser des membranes auto-supportée, de faible épaisseur (e = 100 µm) et de haute conductivité ionique. Les deux premières stratégies de synthèse, basé respectivement sur la préparation de réseaux de poly(1,2,3-triazolium)s et sur la réticulation de copolysiloxanes, n’ayant pas permis d’obtenir de matériaux avec des propriétés satisfaisantes, des films de polyacrylates contenant des liquides ioniques imidazoliums ont été développés. Grâce à l’insertion de hauts taux de cette phase liquide à l’intérieur de ces ionogels, jusqu’à 70 w%, des conductivités supérieures à 10-3 S cm-1 à 30°C ont pu être atteintes, tout en gardant une bonne tenue mécanique à faible épaisseur. Ces électrolytes ont pu être caractérisés électrochimiquement et ont démontré qu’ils permettaient de préparer des cellules supercapacitives fonctionnelles. Cependant, les faibles capacités obtenues indiquent un faible remplissage de la porosité des électrodes, qui est limitant pour l’échange des charges. La poursuite de ces travaux est donc nécessaire pour optimiser ces matériaux, ainsi que les montages utilisés, mais ces gels s’avèrent malgré tout prometteurs et ont pu permettre de préparer des cellules de dimensions équivalentes aux systèmes commerciaux / In order to offer an alternative to the supercapacitors based on aqueous liquid electrolytes that are produced by Hutchinson, this thesis has focused on the development of ionic gels composed of crosslinked polymers containing an ionic liquid phase, that can be used as electrolytes. So, the goal of this study has been to synthesize self-supported thin films (e = 100 µm) with high ionic conductivity.The first two synthesis strategies, respectively based on poly(1,2,3-triazolium)s networks and the crosslinking of polysiloxanes copolymers, did not lead to materials with satisfying properties for this application. So, a third synthesis pathway, based on the copolymerization of acrylate monomers in the presence of imidazolium ionic liquids was developed. As these ionogels were able to contain as much as 70 w% of this liquid phase, ionic conductivities of up to 10-3 S cm-1 at 30°C were obtained, while maintaining good mechanical stability at very low thickness. These electrolytes were characterized by electrochemical measures, and displayed the ability to function inside supercapacitive cells. However, low specific capacities were obtained, indicating that the electrodes’ porosity is only partially filled. Further work is necessary for the optimization of these ionogels, as well as the adaptation of the cells’ components, but these materials showed good potential nevertheless, as they allowed the preparation of functioning cells with the same dimensions as commercial devices

The growing renewable energy consumption has stimulated the rapid development of diverse energy storage systems (ESSs) in our electronic society. As a successful representative, lithium-ion batteries (LIBs) play a vital role in meeting today's energy storage demand. However, LIBs are plagued by intrinsic unsafety and detrimental environmental contamination. In this respect, rechargeable aqueous zinc-ion batteries (ZIBs) and supercapacitors (SCs) as potential alternatives have attracted considerable attention due to their characteristics such as innate safety, environmental friendliness, cost-effectiveness, competitive gravimetric energy density, and loose fabrication process. Inspired by these merits, massive efforts have been devoted to designing and exploring high-performance aqueous Zn-based energy storage devices. The key for advanced Zn-based energy storage devices is to exploit high-performance cathode materials. Covalent organic frameworks (COFs) are an emerging class of organic polymer with periodic skeletons showing attractive properties in structural tunability, well-defined porosity, functional versatility, and high chemical stability. The distinguishing features of COFs make them promising electrode materials for electrochemical energy storage applications. However, the electrochemical storage capability and charge storage mechanism of COF materials have been rarely investigated, and their potential applications have not been evaluated yet so far. In this thesis, COFs are proposed as cathode materials for rechargeable aqueous Zn-ion energy storage. Initially, a new phenanthroline COF (PA-COF) material was synthesized and used as an electrode for Zn-ion supercapatteries (ZISs) for the first time. The as-synthesized PA-COF shows abundant nucleophilic sites and suitable pore structure, demonstrating the efficient storage capability of Zn2+ and H+. Further, hexaazatriphenylene-based COF (HA-COF) material with and without precisely grafted quinone functional groups has been proposed to understand structure-activity relationships. In this chapter, the influence of quinone groups on the electrochemical performance of HA-COF has been systematically studied, disclosing an enhancement coordination capability of Zn ions against protons in the quinone-functionalized HA-COF. Lastly, we synthesized a radical benzobisthiazole COF (BBT-COF) and deeply investigated the electrochemical performance. As expected, this COF electrode shows an ultrastable cycling performance and demonstrates a radical reaction pathway.

Summary Combination of PANI and the cost-effective graphite can obtain composites with good electrochemical performance. For the synthesis method of in-situ polymerization of aniline in presence of GNP, the type and content of oxidant can affect the electrochemical properties of PANI/GNP composites. Besides, the addition of excess dopant can influence the electrochemical properties of a PANI-dominated system. The two eco-friendly reduction ways, namely polymerization of dopamine and adding TA, both produced graphite with good dispersion stability and enhanced interaction with PANI. But the reduction effect of dopamine polymerization was weak, and the non-conductivity of PDA has negative effect on the electrochemical performance of the composites. Using the environmental friendly TA is an effective and facile way to produce cost-effective PANI/graphite composites for supercapacitor purpose. Comparing the two types of graphite, rGO showed lower conductivity and more defects in the carbonaceous structure compared to GNP. In my study, the PANI/(GNP-TA) (1:0.1) composites, which was prepared by using APS as oxidant and without dopant, exhibited the highest capacitive ability. In a three-electrode testing system, the PANI/(GNP-TA) composite showed a high specific capacitance of 351.2 F g-1 at 10 mV s 1. The corresponding two-electrode solid-state supercapacitor device exhibited a promising energy density of 2.3 Wh kg-1 at 0.5 A g-1, which was comparable to the commercially available supercapacitors (around 5 Wh kg-1). But for application the rate capability of the composite needs to be enhanced, in order to maintain the good capacitive performance at high current density.

Energy storage provides sustainability when coupled with renewable but intermittent energy sources such as solar, wave and wind power, and electrochemical supercapacitors represent a new storage technology with high power and energy density. For inclusion in supercapacitors, transition metal oxide and sulfide electrodes such as RuO2, IrO2, TiS2, and MoS2 exhibit rapid faradaic electron–transfer reactions combined with low resistance. The pseudocapacitance of RuO2 is about 720 F/g, and is 100 times greater than double-layer capacitance of activated carbon electrodes. Due to the two-dimensional layered structure of MoS2, it has proven to be an excellent electrode material for electrochemical supercapacitors. Cathodic electrodeposition of MoS2 onto glassy carbon electrodes is obtained from electrolytes containing (NH4)2MoS4 and KCl. Annealing the as-deposited Mo sulfide deposit improves the capacitance by a factor of 40x, with a maximum value of 360 F/g for 50 nm thick MoS2 films. The effects of different annealing conditions were investigated by XRD, AFM and charge storage measurements. The specific capacitance measured by cyclic voltammetry is highest for MoS2 thin films annealed at 500°C for 3h and much lower for films annealed at 700°C for 1 h. Inclusion of copper as a dopant element into electrodeposited MoS2 thin films for reducing iR drop during film charge/discharge is also studied. Thin films of Cu-doped MoS2 are deposited from aqueous electrolytes containing SCN-, which acts as a complexing agent to shift the cathodic Cu deposition potential, which is much more anodic than that of MoS2. Annealed, Cu-doped MoS2 films exhibit enhanced charge storage capability about 5x higher than undoped MoS2 films. Coal combustion is currently the largest single anthropogenic source of CO2 emissions, and due to the growing concerns about climate change, several new technologies have been developed to mitigate the problem, including oxyfuel coal combustion, which makes CO2 sequestration easier. One complication of oxyfuel coal combustion is that corrosion problems can be exacerbated due to flue gas recycling, which is employed to dilute the pure O2 feed and reduce the flame temperature. Refractory metal diffusion coatings of Ti and Zr atop P91 steel were created and tested for their ability to prevent corrosion in an oxidizing atmosphere at elevated temperature. Using pack cementation, diffusion coatings of thickness approximately 12 and 20 µm are obtained for Ti and Zr, respectively. The effects of heating to 950°C for 24 hr in 5% O2 in He are studied in situ by thermogravimetric analyses (TGA), and ex situ by SEM analyses and depth profiling by EDX. For Ti-coated, Zr-coated and uncoated P91 samples, extended heating in an oxidizing environment causes relatively thick oxide growth, but extensive oxygen penetration greater than 2.7 mm below the sample surface, and eventual oxide exfoliation, are observed only for the uncoated P91 sample. For the Ti- and Zr-coated samples, oxygen penetrates approximately 16 and 56 µm, respectively, below the surface. In situ TGA verifies that Ti-and Zr-coated P91 samples undergo far smaller mass changes during corrosion than uncoated samples, reaching close to steady state mass after approximately four hours.