archives@tulane.edu / 1 / Madhu Sudan Gaire

Denna rapport undersöker om superkondensatorer kan ersätta en energireserv bestående av batterier i en befintlig produkt. Bakomliggande teori av superkondensatorn redovisas samt dess användning som energireserv i lågvoltssystem. En krets konstrueras och testas för att verifiera funktionen. Simuleringar utförs för att verifiera valen till kretsen. Matlab och LTSpice används för simuleringarna. Kretsen skapas i OrCad och Altium Designer. Teorin, simuleringarna och testerna pekar på att superkondensatorer kan ersätta batterierna samt att de ställda kraven går att uppfylla. Alla tester gav dock inte resultat och därför kunde inte alla krav verifieras. Framtida tester behövs för att kunna garantera att lösningen kan uppfylla livslängds- och temperaturkraven eller om det behövs bytas till superkondensatorer med större kapacitet. / This report examines if supercapacitors could replace the existing batteries used in a product as a power source. The theory of supercapacitors and the use of these as a power source in low volt systems is presented. A circuit was created and tested to verify the function. Simulations were performed to verify the choices for the circuit. Matlab and LTSpice was used for the simulations. The circuit was created using OrCad and Altium Designer. The theory, simulations and tests all pointed towards that indeed supercapacitors can replace the existing batteries and the requirements can be met. Although not all tests resulted in results, therefore not all of the requirements could be verified. Future tests are needed to be able to guarantee that the solution can meet the lifetime and temperature requirements or if it will be necessary to replace the supercapacitors with ones that have higher capacity.

Electrochemical Supercapacitors (ES), also known as Supercapacitor or Ultracapacitor, has been regarded as an advanced electrical energy storage device for decades. Fabrication of advanced electrode materials is of critical importance for advanced ES. Among various materials used for ES electrode, polypyrrole (PPy) is found to be a promising material due to high specific capacitance, good electrical conductivity, low cost and ease of processing. The use of advanced anionic dopants and addition of multiwall carbon nanotube (MWCNT) have been proved an .effective approach towards advanced PPy based ES with improved electrochemical behaviors. In this research, chemical polymerization of PPy powders and PPy/MWCNT composite materials have been successfully accomplished in presence of advanced anionic dopants, including chromotrope families, amaranth, pyrocatechol violet, eriochrome cyanine R and acid fuchsin. The influence of polyaromatic dopants with different molecular size, charges and charge to mass ratios on the microstructure and electrochemical characteristics has been discussed. PPy coated MWCNT with uniform microstructures was successfully achieved in simple chemical methods. The results showed PPy powders with enhanced microstructures and electrochemical behaviors can be obtained by using such advanced anionic dopants. Multi-charged polyaromatic dopants with larger molecular size benefitted PPy powders with smaller particle size, improved specific capacitance, and enhanced cycling stability, at high electrode mass loadings. Moreover, advanced aromatic dispersant and chemical synthesis was proved a simple and effective method for fabrication of PPy/MWCNT composite materials at different PPy/MWCNT mass ratio, among which the powder with PPy/MWCNT mass ratio of 7:3 showed optimum electrochemical performance. Last but not the least, the use of advanced high porosity current collector (Ni foam) allowed high electrode mass loading and good electric conductivity. As a result, advanced PPy/MWCNT composite materials which allows improved electrochemical behaviors, especially at high mass loading, are promising electrode materials for ES. / Thesis / Master of Applied Science (MASc)

Ti3C2Tx MXene has gained significant attention for biosensor and supercapacitor applications because of 1) its metallic conductivity, large surface area, and reversible surface redox reactions led to high pseudocapacitance and high-rate performance; 2) the unique 2D morphology and high biocompatibility drive great motivation to design advanced nanohybrid systems with bio-receptors; 3) the high density of surface functional groups offers improved biomolecule loading and flexibility for further functionalization. In this thesis, biosensors and electrochemical energy storage devices based on Ti3C2Tx MXene are proposed. Specifically, Ti3C2Tx nanosheets were uniformly functionalized with aminosilane to provide a covalent binding for the immobilized bio-receptor (anti-CEA) for label-free ultrasensitive detection of cancer biomarker (CEA). [Ru(NH3)6]3+ is discovered as the preferable redox probe for biosensing. The fabricated MXene-based sensor exhibits a more comprehensive linear detection range and high sensitivity. Further, Ti3C2Tx nanosheets were introduced as the transducer, and Ti3C2Tx /Prussian blue (Ti3C2Tx/PB) composite was synthesized for sensitive detection of hydrogen peroxide. Meanwhile, a one-step patterning process for highly conductive nitrogen-doped laser-scribed graphene (N-LSG) has been developed. Working electrodes (Ti3C2Tx/PB/N-LSG) were extended by using different enzymes for corresponding biomarker detection, namely glucose, lactate, and alcohol. The enzyme/Ti3C2Tx/PB/N-LSG electrodes exhibit significantly improved electrocatalytic activity and outperform previously reported on-chip graphene-based biosensors. Further, a stretchable, wearable, and multifunctional Ti3C2Tx-based biosensor were designed for durable and sensitive detection of biomarkers in sweat. A unique modular design enabled a simple exchange of the specific sensing electrode to target the desired analytes, while an implemented three-phase interface design for the constant supply of oxygen led to superior sensor performance and stability. As expected, during in-vitro perspiration monitoring of human subjects, the physiochemistry signals (glucose and lactate level) could be measured simultaneously with high sensitivity and good repeatability, outperforming traditional reported graphene/PB- and CNTs/PB-based biosensors. Finally, we developed an in-plane hybrid microsupercapacitor, employing battery-type CuFe-Prussian blue analog (CuFe-PBA) as the positive electrode and pseudocapacitive Ti3C2Tx as the negative electrode. Due to the excellent match of the two types of high-rate performance materials in proton-based electrolyte, the designed on-chip device achieved excellent electrochemical performance.

Global efforts to reduce greenhouse gas emissions, particularly CO2, have led countries to focus on decarbonizing the transportation sector. Moving towards electric vehicles (EVs) is necessary to reduce emissions, however despite EV technological advancements they have shortcomings in both performance and longevity. Supercapacitors are similar to batteries, however their ability to easily charge and discharge at much higher rates makes them excellent devices to work in tandem with batteries to advance their collective performance capabilities in EVs. Traditional metal-based supercapacitor materials remain to be high cost, non-renewable, and often environmentally toxic. On the other hand, quinones are organic materials considered as promising candidates for organic electrodes due to the redox activity, low cost, ease of structural modifications, nontoxicity, and renewability. To overcome quinone challenges with low electrical conductivity and dissolution in electrolyte, polymerizing quinones has become a popular modification. Conducting polymers (CPs) are increasing in interest as their -conjugated structures provide efficient electron transfer and good electrical conductivity. In the work of this master’s thesis, two types of materials were developed for supercapacitor applications; a polyimide made from alternating units of the quinones 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and 2,6-diaminoanthraquinone (DAAQ) known as poly-perylene-3,4,9,10-tetracarboxydiimide-anthraquinone (PPA), and a truncated analogue of PPA comprised of PTCDA and two molecules of 2-diaminoanthraquinone (2-AAQ), termed N,N′-bis(2-anthra-quinone)]-perylene-3,4,9,10- tetracarboxydiimide (PDI-DAQ). All the original redox-active sites were retained following a facile synthesis to achieve fast multi-electron transfer mechanisms. These materials both were used to prepare composite electrodes with a low-cost carbon black (Ketjenblack) via simple and scalable preparation methods. Capacitances reached up to 377 F/g at 5 mV s-1 with a capacitance retention of 63.9% after 10,000 cycles at 100 mV/s. This work demonstrates the impressive energy storage capabilities of novel organic molecules in supercapacitors with low-cost carbon black to improve the performance of next-generation EVs. / Thesis / Master of Applied Science (MASc) / Worldwide efforts to reduce greenhouse gas emissions, like CO2, have made the world focusing on making more environmentally sustainable transportation methods, such as switching to electric vehicles (EVs). However, EVs still face performance and longevity issues due to the limitations of the batteries used. Batteries are not designed to charge and discharge quickly, however supercapacitors, which are like batteries, can charge and discharge much faster, making them a great match to incorporate into EVs alongside batteries. Traditional metal supercapacitor materials are costly and non-sustainable, but organic molecules like quinones offer a much cheaper, sustainable solution. Modifying quinones along with the addition of cheap carbon additives can vastly improve its energy storage performance and long-term usage. With future scalability in mind, this work demonstrates the potential for organic materials to potentially be used to enhance the performance of next generation EVs.

Supercapacitors (or electric double-layer capacitors) are high power energy storage devices that store charge by the non-faradaic adsorption of ions at the interface between porous carbon electrodes and an electrolyte solution. The development of new electrode materials and electrolytes with improved performances is an active area of research today, yet there are relatively few studies of the molecular mechanisms of the charge storage process. In this work, nuclear magnetic resonance (NMR) spectroscopy is developed for the study of the charge storage mechanisms of supercapacitors. Importantly, NMR experiments show that electrolyte ions adsorbed inside the pores of the carbon electrodes can be resolved from those in bulk electrolyte for a range of supercapacitor electrode materials. Chemical shift calculations show that the adsorbed species are subject to ring current effects, whereby the delocalised electrons in the carbon shield the nearby nuclei. The calculated effects depend on the local carbon structure, helping to rationalise the variations observed when different porous carbons are studied experimentally, and allowing structural information to be extracted from the spectra. NMR experiments performed on electrodes extracted from ionic liquid-based supercapacitors with different applied voltages allow the numbers of adsorbed ions to be measured upon charging. It is shown that supercapacitor charging involves the migration of both anions and cations in and out of the carbon pores in each electrode, with the anions dominating the charge storage process. When combined with lineshape measurements, which offer information about the diffusion of adsorbed ions, the power performances of supercapacitor devices with different electrolytes are rationalised. In situ NMR methods are then developed to allow mechanistic studies of working supercapacitors as they are charged and discharged inside the NMR magnet. The experiments reveal that the charge storage mechanism depends on both the electrolyte and the electrode material studied. During charging, reversible chemical shift changes are also observed, arising from the introduction of paratropic ring currents. Finally, cross polarisation experiments allow the selective observation of the adsorbed electrolyte species, and show that their motion slows down during supercapacitor charging. Overall, the NMR approach offers unique insights into the molecular mechanisms of the supercapacitance phenomenon.

A combination of high prices of fossil fuels and the increased awareness of their negative environmental impact has influenced the development of new cleaner energy sources. Among various viable technologies, fuel cells have emerged as one of the most promising sources for both portable and stationary applications. Fuel cell stacks produce DC voltage with a 2:1 variation in output voltage from no load to full load conditions. Hence, to increase the utilization efficiency and system stability, a power conditioner consisting of DC-DC and DC-AC converters is required for load interface. The design of power conditioners is driven by the application. This dissertation presents several different solutions for applications ranging from low-power portable sources for small electronics and laptop computers to megawatt-power applications for fuel cell power plants. The design and analysis for each power conditioner is presented in detail and the performance is verified using simulations and prototypes. Special consideration is given to the role of supercapacitors who act as the additional energy storage elements. It is shown that the supercapacitor connected at the terminals of a fuel cell can contribute to increased steady state stability when powering constant power loads, improved transient stability against load transients, and increased fuel efficiency (i.e. reduced hydrogen consumption).

Graphene has been extensively studied for possible future technical applications due to its unique electronic, transport, and mechanical properties. For practical applications, graphene often needs to be placed in a medium or on a substrate. The interfacial interaction between graphene and other materials can greatly affect the performance of graphene-based devices, but has not been well explored. My thesis research focused on developing a better understanding of the interface of pristine and chemically/mechanically modified graphene sheets with ionic liquids (ILs) as well as amorphous silica (a-SiO₂) surfaces using first principles-based atomistic modeling which combines density functional theory, classical molecular dynamics, and Metropolis Monte Carlo. The major focus of my thesis research was on investigating the interfacial structure and capacitance between graphene and ILs; graphene-based materials and ILs have been regarded as viable candidates for supercapacitor electrodes and electrolytes, respectively. Particular emphasis was placed on elucidating the relative contributions of the electric double layer (EDL) capacitance at the graphene/IL interface and the quantum capacitance of graphene-like electrodes. More specifically, we first determined the microstructure (such as orientation, packing density, cation-anion segregation) of chosen ILs near planar graphene electrodes with various surface charge densities. Based on the calculated IL microstructure for each system, the EDL capacitance was then evaluated with particular attention to the effect of cation-anion size difference. We also examined the influence of the chemical and mechanical modifications of graphene-like electrodes on the supercapacitor performance. Especially, mechanisms underlying chemical doping-induced enhancement of the total interfacial capacitance were addressed through analysis of electrode quantum capacitance changes resulting from electronic structure modifications. A part of my effort was also devoted to examining the binding interaction of graphene with a-SiO₂ (which is not yet clearly understood despite its scientific and technological importance). In particular, we attempted to evaluate quantitatively the adsorption strength of graphene on the a-SiO₂ surface, which has been under debate mainly due to the difficulty of direct measurement. / text

RuO2/carbon composites have attracted a lot of attention for use as supercapacitor electrodes due to their high power and energy capabilities. Methods for loading the RuO2 into the carbon include impregnation and electrochemical deposition. The first project involves impregnation of RuO2 nanoparticles into a mesoporous carbon powder. Structural changes of the RuO2 nanoparticles in the composite were induced by annealing at high temperatures, and X-ray diffraction (XRD) and X-ray absorption (XAS) were used to study the changes. In situ electrochemical-XAS experiments were also developed and performed to study the structural stability of the RuO2 nanoparticles in the composite as well as bulk RuO2•xH2O, with respect to changing potential. Preliminary work on the electrodeposition of RuO2•xH2O onto Au foil and carbon cloth was performed. An electrode with a high specific capacitance of the RuO2•xH2O component was achieved. However, further studies need to be performed to optimize the deposition solution.

Electrochemical capacitors (ECs) have drawn much attention owing to their fast charging/discharging rate, and long lifetime up to millions of cycles. Applications of EC range from large scale transportation to miniaturized electronics. The research reported herein explores the development of an economical process for the synthesis of high performance electrode material for high power ECs. A two stage synthesis process which consists of electroplating of molybdenum oxide followed by thermal nitridation was developed. X-ray diffraction and X-ray photoelectron spectroscopy revealed the material to be Mo oxide with nitrogen substitution, Moz(O,N). In a three electrode system, the Moz(O,N) electrodes showed capacitance as high as 16 mF/cm2. Symmetric EC cells achieved state of the art time constant of 100 ms. Ultrahigh power ECs were demonstrated for the first time using Moδ(O,N) electrodes and SiWA-H3PO4-PVA electrolyte, achieving with 10 ms time constant one of the lowest time constants reported for EC.