In electrode double layer capacitor (EDLC), electrodes usually contain binder materials to provide adhesion between electrode materials. However, binder materials usually bring unwanted resistances to the component due to their non-conductivity properties and the occupation of ion cavities. The purpose of this thesis is to demonstrate the feasibility of fabricating electrodes for EDLCs by using carbon nanotubes (CNTs) and graphene oxide (GO) without using any binding materials. At the same time, investigating the binder-free electrode’s electrochemical properties and make an assumption of its potential application in the future. The slurry of binder-free electrodes was fabricated by ultrasonicating water suspended CNTs and GO aqueous solution. The ultrasonicated mixture was then casted on an aluminum foil, followed by drying processes to form into an electrode film. By combining the CNTs/GO binder-free electrodes with aqueous electrolyte, a symmetrical electrode double layer capacitor (EDLC) was fabricated. The EDLC was also tested for electrochemical performance using a polyvinyl alcohol (PVA) based gel electrolyte. It was found that an electrode with a low resistance was achieved by eliminating the use of binders. The as-prepared sample had an equivalent series resistance (ESR) of 0.07 Ohms. Furthermore, a solid-state, binder-free EDLC sample achieved a specific capacitance of 0.2876 F/m2 in volumetric terms, or 58.24 mF/g in gravimetric terms. The laboratorial investigation demonstrates a possible scheme of decreasing resistance start with eliminating binding materials in electrodes. Successfully fabricated binder-free electrodes show the feasibility of eliminating binding materials in electrodes. The easy access fabrication process of graphene oxide/CNT electrodes provides a chance for mass production in the industry. Solid-state electrolyte samples also give an example of making all-solid-state energy storage devices.

A demanda crescente por meios de armazenar eficientemente energia elétrica tem incentivado a busca de materiais que melhorem o desempenho específico de dispositivos armazenadores de carga elétrica. Dentre os materiais a base de carbono, destaca-se o grafeno e seus derivados como tendo grande potencial para aumentar o desempenho de tais. Nesse trabalho, estudam-se duas abordagens para a imobilização de grafeno sobre condutores metálicos e o efeito que essas tem na eletroquímica dos sistemas. De maneira geral, evitou-se a utilização de polímeros como aglutinantes na construção de eletrodos, visto que esses podem interferir negativamente na eletroquímica do sistema (além de não serem condutores elétricos, não têm nenhum benefício em relação a aumento de capacitância do eletrodo). As metodologias estudadas podem ser separadas em duas categorias, sendo essas a de eletrodos obtidos por deposição eletroforética de derivados de grafeno e imobilização de grafeno sobre condutores metálicos pelo uso de camadas orgânicas, que servem de ponto de ancoragem para os derivados de grafeno. Os eletrodos foram então caracterizados eletroquimicamente, visando principalmente seu uso em capacitores eletroquímicos. Dentre as técnicas utilizadas para tal, destacam-se o uso de voltametria cíclica e espectroscopia de impedância eletroquímica, além de técnicas não eletroquímicas como espectroscopia Raman, microscopia eletrônica de varredura, microscopia de força atômica e microbalança de cristal de quartzo. De modo geral, pode-se observar que a deposição eletroforética é uma maneira simples de obter eletrodos modificados, e apresenta alta reprodutibilidade. O fato de não possuírem outros compostos químicos que não o grafeno, além de serem altamente rugosos, mostrou que esses eletrodos tem desempenho capacitivo muito bom, sendo o método de obtenção do grafeno e a maneira escolhida para deposição diretamente responsáveis pela morfologia obtida. A construção de eletrodos pela ancoragem de grafeno foi feita com base na (eletro)química de sais de diazônio, que se mostrou bastante promissora quanto a capacidade de se obter uma ligação química estável entre as folhas de grafeno e o metal. A alta reatividade dos sais de diazônio, no entanto, se mostrou danosa a eletroquímica do grafeno, sendo que tais eletrodos não apresentaram nenhuma característica que justificasse seu uso em capacitores eletroquímicos. Assim, os avanços e desafios restantes em relação a essas abordagens na construção capacitores eletroquímicos com alto desempenho específico encontram-se aqui detalhados. / The increasing demand for efficient electrical energy storage devices has pushed research towards materials with potential to increase the specific performance of such devices. Among the carbon-based materials, one that has been heavily studied as a potential candidate to accomplish such feat is graphene and its chemical derivatives. In this work, two methodologies to accomplish graphene immobilization over metallic current collectors are approached, as well as the effects that such approaches have on the electrochemistry of the resulting electrodes. As a general guideline, the usage of polymeric binders as ways of keeping good mechanical stability are avoided, due to their tendency to negatively impact the system\'s electrochemistry (not only they\'re normally electrical in sulators, they also don\'t usually possess any intrinsic electroactivity that could enhance the electrode\'s capacitance). The methodologies in study can be separated into two categories, namely, electrophoretic deposition and usage of organic molecules as anchoring points to attach graphene sheets to the surface. Such electrodes were characterized by a number of electrochemical technics, most prominently cyclic voltammetry and electrochemical impedance spectroscopy in the group of electrochemical technics, and Raman spectroscopy, atomic force microscopy, scanning electron microscopy and quartz crystal microbalance in the group of non-electrochemical technics. Electrophoretic deposition of graphene is proved to be a very straightforward and reproducible way to obtain modified electrodes. Since no chemical compound other than the graphene derivatives are necessary, and that the final electrodes have very rough surfaces, such electrodes have very high capacitance, and those characteristics are direct consequence of the chosen method. Anchoring graphene derivatives on the surface of metallic conductors by the (electro)-chemistry of diazonium salts is shown to be a promising method to achieve strongly bound graphene sheets to a surface. The high reactivity of diazonium salts, though, hampers the electrochemical activity of graphene, and no electrodes suitable to be used in electrochemical capacitors were obtained. In summary, the advances and remaining challenges towards the use of such methodologies in the construction of electrochemical capacitors are presented here.

A demanda crescente por meios de armazenar eficientemente energia elétrica tem incentivado a busca de materiais que melhorem o desempenho específico de dispositivos armazenadores de carga elétrica. Dentre os materiais a base de carbono, destaca-se o grafeno e seus derivados como tendo grande potencial para aumentar o desempenho de tais. Nesse trabalho, estudam-se duas abordagens para a imobilização de grafeno sobre condutores metálicos e o efeito que essas tem na eletroquímica dos sistemas. De maneira geral, evitou-se a utilização de polímeros como aglutinantes na construção de eletrodos, visto que esses podem interferir negativamente na eletroquímica do sistema (além de não serem condutores elétricos, não têm nenhum benefício em relação a aumento de capacitância do eletrodo). As metodologias estudadas podem ser separadas em duas categorias, sendo essas a de eletrodos obtidos por deposição eletroforética de derivados de grafeno e imobilização de grafeno sobre condutores metálicos pelo uso de camadas orgânicas, que servem de ponto de ancoragem para os derivados de grafeno. Os eletrodos foram então caracterizados eletroquimicamente, visando principalmente seu uso em capacitores eletroquímicos. Dentre as técnicas utilizadas para tal, destacam-se o uso de voltametria cíclica e espectroscopia de impedância eletroquímica, além de técnicas não eletroquímicas como espectroscopia Raman, microscopia eletrônica de varredura, microscopia de força atômica e microbalança de cristal de quartzo. De modo geral, pode-se observar que a deposição eletroforética é uma maneira simples de obter eletrodos modificados, e apresenta alta reprodutibilidade. O fato de não possuírem outros compostos químicos que não o grafeno, além de serem altamente rugosos, mostrou que esses eletrodos tem desempenho capacitivo muito bom, sendo o método de obtenção do grafeno e a maneira escolhida para deposição diretamente responsáveis pela morfologia obtida. A construção de eletrodos pela ancoragem de grafeno foi feita com base na (eletro)química de sais de diazônio, que se mostrou bastante promissora quanto a capacidade de se obter uma ligação química estável entre as folhas de grafeno e o metal. A alta reatividade dos sais de diazônio, no entanto, se mostrou danosa a eletroquímica do grafeno, sendo que tais eletrodos não apresentaram nenhuma característica que justificasse seu uso em capacitores eletroquímicos. Assim, os avanços e desafios restantes em relação a essas abordagens na construção capacitores eletroquímicos com alto desempenho específico encontram-se aqui detalhados. / The increasing demand for efficient electrical energy storage devices has pushed research towards materials with potential to increase the specific performance of such devices. Among the carbon-based materials, one that has been heavily studied as a potential candidate to accomplish such feat is graphene and its chemical derivatives. In this work, two methodologies to accomplish graphene immobilization over metallic current collectors are approached, as well as the effects that such approaches have on the electrochemistry of the resulting electrodes. As a general guideline, the usage of polymeric binders as ways of keeping good mechanical stability are avoided, due to their tendency to negatively impact the system\'s electrochemistry (not only they\'re normally electrical in sulators, they also don\'t usually possess any intrinsic electroactivity that could enhance the electrode\'s capacitance). The methodologies in study can be separated into two categories, namely, electrophoretic deposition and usage of organic molecules as anchoring points to attach graphene sheets to the surface. Such electrodes were characterized by a number of electrochemical technics, most prominently cyclic voltammetry and electrochemical impedance spectroscopy in the group of electrochemical technics, and Raman spectroscopy, atomic force microscopy, scanning electron microscopy and quartz crystal microbalance in the group of non-electrochemical technics. Electrophoretic deposition of graphene is proved to be a very straightforward and reproducible way to obtain modified electrodes. Since no chemical compound other than the graphene derivatives are necessary, and that the final electrodes have very rough surfaces, such electrodes have very high capacitance, and those characteristics are direct consequence of the chosen method. Anchoring graphene derivatives on the surface of metallic conductors by the (electro)-chemistry of diazonium salts is shown to be a promising method to achieve strongly bound graphene sheets to a surface. The high reactivity of diazonium salts, though, hampers the electrochemical activity of graphene, and no electrodes suitable to be used in electrochemical capacitors were obtained. In summary, the advances and remaining challenges towards the use of such methodologies in the construction of electrochemical capacitors are presented here.

Cette thèse a consisté en la fabrication d’électrodes de charbon actif frittées par SPS destinées aux supercondensateurs à double couche électrochimique. L’influence des paramètres de frittage (température, pression, durée du palier isotherme et vitesses de chauffe et de refroidissement) sur les propriétés structurales et microstructurales des pastilles de charbon actif a été évaluée par diffraction des rayons X, microscopie électronique à balayage et en transmission, spectrométrie de photoélectrons X, mesures de surface spécifique et de volume microporeux et détermination des propriétés mécaniques. Les performances électrochimiques des pastilles de charbon actif frittées sélectionnées pour leurs bonnes propriétés de volume microporeux, de résistance mécanique à l’électrolyte et de masse volumique élevée ont été déterminées par mesures galvanostatiques et de spectrométrie d’impédance. Un gain en capacité volumique de 31% a été obtenu pour un supercondensateur composé d’électrodes de charbon actif pur de 200 μm d’épaisseur frittées à 1100°C – 50 MPa par rapport à un supercondensateur composé d’électrodes de production de Blue Solutions. Cependant sa résistance série est deux fois supérieure à celle d’un supercondensateur de production de volume identique. Des résultats prometteurs de frittage multi-pastilles, possédant des propriétés microstructurales proches, indiquent une voie possible d’industrialisation du procédé SPS pour la fabrication d’électrodes frittées de charbon actif destinées aux supercondensateurs. / This thesis has consisted in the manufacturing of activated carbon electrodes sintered by SPS for Electric Double-Layer Capacitors (EDLCs). The influence of sintering parameters (temperature, pressure, isothermal dwell duration, heating and cooling rates) on structural and microstructural properties of sintered activated carbon pellets has been evaluated by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectrometry, specific area and microporous volume measurements and determination of mechanical properties. The electrochemical performances of sintered activated carbon pellets selected for their good properties in terms of microporous volume, mechanical resistance in the electrolyte and high density were determined by galvanostatic and impedance spectrometry measurements. A 31% increase of the volumetric capacity was obtained for a supercapacitor composed of 200 μm thick electrodes of pure activated carbon sintered at 1100°C – 50 MPa, relative to a supercapacitor composed of industrial electrodes from Blue Solutions company. However, its serial resistance is twice larger than that of an industrial of identical volume. Promising results of multi-pellet sintering, possessing close microstructural properties, indicate a possible way of industrialization of SPS process for the manufacturing of sintered activated carbon electrodes for supercapacitors.

Over-the-air programming systems for wireless sensor networks have drawbacks that stem from fundamental limitations in the hardware used in current sensor nodes. Also, advances in technology make it feasible to use capacitors as the sole energy storage mechanism for sensor nodes using energy harvesting, but most current designs require additional electronics. These two considerations led to the design of a new sensor node. A microcontroller was chosen that meets the Popek and Goldberg virtualization requirements. The hardware design for this new sensor node is presented, as well as a preliminary operating system. The prototypes are tested, and demonstrated to be sustainable with a capacitor and solar panel. The issue of capacitor leakage is considered and measured.

Porous carbon derived from an inorganic silicon carbide (SiC) precursor, termed SiC-derived carbon, is an attractive material for electrochemical energy storage applications, including electrodes for electrical double layer capacitors (EDLCs). The objective of this thesis is to investigate the effects that the carbide-derived carbon (CDC) microstructure and pore structure have on the energy and power characteristics of the EDLC electrodes. Conventional SiC CDC is produced from non-porous crystalline SiC powder at temperatures above 800 °C. Here we studied the performance of SiC CDCs produced by chlorination at 700-900 °C of an ordered mesoporous SiC precursor, which was synthesized via a 1000 °C pyrolysis of polycarbosilane infiltrated into an SBA-15 silica template having ordered mesopores. The SiC CDC was purified from chlorine impurities by annealing in ammonia. The surface area and pore size of the purified SiC CDC was characterized via N2 and CO2 sorption using density functional theory (DFT) and Brunnauer, Emmet, and Teller (BET) theory. The specific capacitance, power and energy densities were characterized via electrochemical measurements of the SiC CDC electrodes in 1 M tetraethylammonium tetrafluoroborate (TEABF4) acetonitrile solution. The SiC CDC exhibited a specific surface area (SSA) in excess of 2400 m2/g and gravimetric capacitance values of up to ~ 150 F/g, among the highest ever reported for any electrodes in this electrolyte. The ordered mesopores allowed for fast ion transport within each particle, resulting in excellent capacity retention under high current rates and ultra-fast frequency response, thus allowing for extremely high power and energy densities. The best overall performance was achieved in SiC CDC samples chlorinated at the lowest temperature of 700 °C.

The focus of this thesis has been to determine the usable voltage range of carbon-based supercapacitors (SC). Supercapacitors are a relatively new type of capacitors with a vast increase in capacitance compared to capacitors which utilize a dielectric as charge separator. A SC consists of two electrodes and an electrolyte separating the electrodes. The charges are stored by electrostatic forces in the interface between the electrode and the electrolyte, forming the so called electrochemical double-layer (EDL). With porous electrodes the effective surface area of the interfacial zone can be made very large, giving SCs a large storage capacity. The limiting factors of a SC is the decomposition potential of the electrolyte and the decomposition of the electrodes. For commercially manufactured SCs the electrolyte is usually an organic solvent, which has a decomposition potential of up to 2.7-2.8 V. Compared to aqueous electrolytes with a thermodynamic limit of 1.23 V. The drawback of using non-aqueous electrolytes is that they are not environmentally friendly, and they increase the production cost. It is claimed that the voltage range can be up to 1.9 V using aqueous electrolytes. Some researchers have focused on aqueous electrolytes for these reasons. In this thesis two different electrolytes were tested to determine if the voltage range could be extended. The experiments were conducted using a three electrode cell and performing cyclic voltammogram measurements (CV). The carbon electrodes were made of  two different sources of grahite, battery graphite or exfoliated graphite, and nano fibrilated cellulose was added to increase the mechanical stability. The results show that the oxidation potential of the carbon electrode was the positive limit. A usable potential of about 1 V was shown. However, when cycling the electrodes to potentials below the decomposition limit, for hydrogen evolution, interesting effects were seen. A decrease in reaction kinetics, indicating a type of conditioning of the electrode was observed. An increase in charge storage capacitance was also observed when comparing the initial measurements with the final, probably corresponding to an increase in porosity. / KEPS projekt Sundsvall Mitt Universitet

Esta dissertação tem por objetivo reportar dados relativos às características elétricas e microestruturais de eletrodos aplicadas em dispositivos armazenadores de energia, especificamente supercapacitores constituídos por eletrodos de carvão ativado. Os parâmetros elétricos estudados foram a resistência em série equivalente obtida pelo método da interrupção de corrente (ESR(Inst)) (sendo que a sigla ESR é oriunda do termo inglês Equivalent Series Resistance), a resistência em paralelo equivalente (EPR(Dep)) obtida pelo método do valor dependente (sendo que a sigla EPR é oriunda do termo inglês Equivalent Parallel Resistance) e a capacitância (C(DC)) obtida pelo método da corrente contínua (sendo que a sigla DC oriunda do termo inglês Direct Current). Tais parâmetros foram escolhidos devido ao impacto que causam no tempo de vida útil, na capacidade de armazenamento de cargas elétricas, na velocidade de carga e descarga, na perda por efeito termoiônico nos processos de carga e descarga e na perda de cargas armazenadas devido à autodescarga em supercapacitores. Os dados microestruturais reportam por meio de imagens a homogeneidade da porosidade e por meio de valores correlacionados a composição química e eventuais contaminações presentes nos eletrodos. Os dados e valores coletados possuem a intenção de servir como referência comparativa de qualidade e apontar qual parâmetro afeta mais a qualidade do supercapacitor. Para tanto foram realizados testes a fim de coletar valores de C(DC), ESR(Inst) e EPR(Dep) após a exposição de supercapacitores de 1F/5,5V a temperaturas de 50ºC, 75ºC, 100ºC e 125ºC por 672 horas, sendo os dados coletados ao inicio dos testes, à temperatura ambiente, e posteriormente a cada 168 horas. Feitos os experimentos concluiu-se que o parâmetro que sofreu maior deterioração com o acréscimo de energia térmica foi a EPR(Dep), em seguida a C(DC), que de fato pouco sofreu alteração e a ESR(Inst), em que a mudança dentro do erro de medição foi imperceptível. / This paper aims to report information on electrical and microstructural characteristics of electrodes applied at devices that store energy, specifically supercapacitors made of activated carbon electrodes. The studied electrical parameters were the equivalent series resistance obtained by the method of the instantaneous value of the voltage drop (ESR(Inst)), where the acronym ESR has the meaning Equivalent Series Resistance, the equivalent parallel resistance (EPR(Dep)) obtained by the method of dependent value, where the acronym EPR has the meaning Equivalent Parallel Resistance, and the capacitance (C(DC)) obtained by the method of direct current. These parameters were chosen because of the impact they have on lifetime, the storage capacity of electric charge, the speed of loading and unloading, the loss thermionic effect on the charge and discharge processes and loss of stored charge due to self-discharge in supercapacitors. The data given by microstructural images of the homogeneity and porosity values correlated by the chemical composition and possible contaminations present in the electrodes. The collected data and values are intended to serve as a comparative reference point and quality parameter which most affects the quality of the supercapacitor. For both tests were carried out in order to collect values of C(DC), ESR(Inst) and EPR(Dep) after supercapacitors of the 1F/5.5V are exposure at temperatures of 50, 75, 100 and 125°C for 672 hours, and the data collected at the beginning of the tests (room temperature) and subsequently every 168 hours. Made experiments it was concluded that the parameter further deterioration suffered with the increase of thermal energy is EPR(Dep), then C(DC), which in fact little changed and ESR(Inst), in which the change in the measurement error was are noticeable.

Esta dissertação tem por objetivo reportar dados relativos às características elétricas e microestruturais de eletrodos aplicadas em dispositivos armazenadores de energia, especificamente supercapacitores constituídos por eletrodos de carvão ativado. Os parâmetros elétricos estudados foram a resistência em série equivalente obtida pelo método da interrupção de corrente (ESR(Inst)) (sendo que a sigla ESR é oriunda do termo inglês Equivalent Series Resistance), a resistência em paralelo equivalente (EPR(Dep)) obtida pelo método do valor dependente (sendo que a sigla EPR é oriunda do termo inglês Equivalent Parallel Resistance) e a capacitância (C(DC)) obtida pelo método da corrente contínua (sendo que a sigla DC oriunda do termo inglês Direct Current). Tais parâmetros foram escolhidos devido ao impacto que causam no tempo de vida útil, na capacidade de armazenamento de cargas elétricas, na velocidade de carga e descarga, na perda por efeito termoiônico nos processos de carga e descarga e na perda de cargas armazenadas devido à autodescarga em supercapacitores. Os dados microestruturais reportam por meio de imagens a homogeneidade da porosidade e por meio de valores correlacionados a composição química e eventuais contaminações presentes nos eletrodos. Os dados e valores coletados possuem a intenção de servir como referência comparativa de qualidade e apontar qual parâmetro afeta mais a qualidade do supercapacitor. Para tanto foram realizados testes a fim de coletar valores de C(DC), ESR(Inst) e EPR(Dep) após a exposição de supercapacitores de 1F/5,5V a temperaturas de 50ºC, 75ºC, 100ºC e 125ºC por 672 horas, sendo os dados coletados ao inicio dos testes, à temperatura ambiente, e posteriormente a cada 168 horas. Feitos os experimentos concluiu-se que o parâmetro que sofreu maior deterioração com o acréscimo de energia térmica foi a EPR(Dep), em seguida a C(DC), que de fato pouco sofreu alteração e a ESR(Inst), em que a mudança dentro do erro de medição foi imperceptível. / This paper aims to report information on electrical and microstructural characteristics of electrodes applied at devices that store energy, specifically supercapacitors made of activated carbon electrodes. The studied electrical parameters were the equivalent series resistance obtained by the method of the instantaneous value of the voltage drop (ESR(Inst)), where the acronym ESR has the meaning Equivalent Series Resistance, the equivalent parallel resistance (EPR(Dep)) obtained by the method of dependent value, where the acronym EPR has the meaning Equivalent Parallel Resistance, and the capacitance (C(DC)) obtained by the method of direct current. These parameters were chosen because of the impact they have on lifetime, the storage capacity of electric charge, the speed of loading and unloading, the loss thermionic effect on the charge and discharge processes and loss of stored charge due to self-discharge in supercapacitors. The data given by microstructural images of the homogeneity and porosity values correlated by the chemical composition and possible contaminations present in the electrodes. The collected data and values are intended to serve as a comparative reference point and quality parameter which most affects the quality of the supercapacitor. For both tests were carried out in order to collect values of C(DC), ESR(Inst) and EPR(Dep) after supercapacitors of the 1F/5.5V are exposure at temperatures of 50, 75, 100 and 125°C for 672 hours, and the data collected at the beginning of the tests (room temperature) and subsequently every 168 hours. Made experiments it was concluded that the parameter further deterioration suffered with the increase of thermal energy is EPR(Dep), then C(DC), which in fact little changed and ESR(Inst), in which the change in the measurement error was are noticeable.

Nanoporous carbons have become a material of interest in many applications such as electrochemical double layer capacitors (supercapacitors). Supercapacitors are being studied for their potential in storing electrical energy storage from intermittent sources and in use as power sources that can be charged rapidly. However, a lack of understanding of the charge storage mechanism within a supercapacitor makes it difficult to optimize them. Two components of this challenge are the difficulties in experimentally characterizing the sub-nanoporous structure of carbon electrode materials and the electrical performance of the supercapacitors. This work provides a means to accurately characterize the porous structure of sub-nanoporus carbon materials and identifies the current limitations in characterizing the electrical performance of a supercapacitor cell. Future work may focus on the relationship between the sub-nano porous structure of the carbon electrode and the capacitance of supercapacitors, and on the elucidation of charge storage mechanisms.